- Synthesis and photosensitizing properties of porphycene with imidazolium tag
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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]).
- Shimakoshi, Hisashi,Sasaki, Kenichi,Iseki, Yusuke,Hisaeda, Yoshio
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- (-)-REGIOLONE, AN α-TETRALONE FROM JUGLANS REGIA: STRUCTURE, STEREOCHEMISTRY AND CONFORMATION
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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.
- Talapatra, Sunil K.,Karmacharya, Bimala,De, Shambhu C.,Talapatra, Bani
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- A luminescent poly(amidoamine)-iridium complex as a new singlet-oxygen sensitizer for photodynamic therapy
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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).
- 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
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- Directing energy transfer in panchromatic platinum complexes for dual Vis-Near-IR or dual visible emission from σ-bonded BODIPY dyes
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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
- Geist, Fabian,Jackel, Andrej,Irmler, Peter,Linseis, Michael,Malzkuhn, Sabine,Kuss-Petermann, Martin,Wenger, Oliver S.,Winter, Rainer F.
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- Porphyrin-Hyperbranched Copolymer Films as Recyclable Photooxidation Catalysts for 1,5-Dihydroxynaphthalene
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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.
- Sun, Kaifang,Guo, Lintong,Cai, Cheng,Hou, Zongsheng,Ren, Qizhi
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- Structure-property relationships and 1O2 photosensitisation in sterically encumbered diimine PtII acetylide complexes
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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
- Nolan, Deanne,Gil, Belen,Wang, Longsheng,Zhao, Jianzhang,Draper, Sylvia M.
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- Green synthetic approaches to furoylnaphthohydroquinone and juglone
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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.
- Benites, Julio,Cortes, Michael,Miranda, Luis,Estela, Cynthia,Rios, David,Valderrama, Jaime A.,Arenas, Jorge
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- Phosphorescent rhenium-dipyrrinates: efficient photosensitizers for singlet oxygen generation
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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
- Manav, Neha,Kesavan, Praseetha E.,Ishida, Masatoshi,Mori, Shigeki,Yasutake, Yuhsuke,Fukatsu, Susumu,Furuta, Hiroyuki,Gupta, Iti
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- Photophysical and photosensitizing properties of brominated porphycenes
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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.
- Shimakoshi, Hisashi,Baba, Tatsushi,Iseki, Yusuke,Aritome, Isao,Endo, Ayataka,Adachi, Chihaya,Hisaeda, Yoshio
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- Green photochemistry: The use of microemulsions as green media in photooxygenation reactions
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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.
- Coyle, Emma E.,Joyce, Kieran,Nolan, Kieran,Oelgemoeller, Michael
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- A study of acridine and acridinium-substituted bis(terpyridine)zinc(ii) and ruthenium(ii) complexes as photosensitizers for O2 ( 1Δg) generation
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The homoleptic zinc(ii) and ruthenium(ii) metal complexes of bis(tridentate) 9-acridine and 10-methyl-9-acridinium-substituted terpyridines were tested for their suitability as triplet photosensitizers (PS) using the photooxidation of 1,5-dihydroxynaphthalene (DHN) to Juglone as a model reaction. Singlet oxygen (O21Δg) generation is superior or comparable to Ru(bpy)32+ for the acridine complexes, whereas the acridinium complexes are ineffective. The molecular structure of the bis(9-(5-([2,2′:6′,2′′-terpyridin]- 4′-yl)thien-2-yl)-10-methylacridinium)zinc(ii) complex ([Zn(MeATT) 2][PF6]4) is determined by X-ray structure analysis, whereas for other complexes DFT calculations were performed for structural parameters to obtain insights into their electronic properties. The Royal Society of Chemistry and Owner Societies.
- Eberhard, Jens,Peuntinger, Katrin,Rath, Susann,Neumann, Beate,Stammler, Hans-Georg,Guldi, Dirk M.,Mattay, Jochen
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- Oxidative phenylamination of 5-substituted 1-hydroxynaphthalenes to N-phenyl-1,4-naphthoquinone monoimines by air and light "on water"
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A number of N-phenyl-1,4-naphthoquinone monoimines 6 - 10 were prepared by on-water oxidative phenylamination of 1,5-dihydroxynaphthalene (1 ) and 5-acetylamino-1-hydroxynaphthalene ( 5 ) with oxygen-substituted phenylamines under aerobic conditions and e
- Benites, Julio,Melndez, Juan,Estela, Cynthia,Ros, David,Espinoza, Luis,Brito, Ivn,Valderrama, Jaime A.
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- Reversible switching of the luminescence of a photoresponsive gadolinium(III) complex
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From blue to red: The structure and luminescence properties of the gadolinium(III) complex 1 were investigated. Reversible switching of the luminescence of 1 in THF at room temperature by alternating light irradiation and O2 exposure is presented, during which the emission color changes as shown in the picture. Light-induced phosphorescence of 1 plays a key role in this behavior. Copyright
- Nakai, Hidetaka,Kitagawa, Kazuhiro,Nakamori, Harutaka,Tokunaga, Taisuke,Matsumoto, Takahiro,Nozaki, Koichi,Ogo, Seiji
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- SPIO@SiO2-Re@PEG nanoparticles as magneto-optical dual probes and sensitizers for photodynamic therapy
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A dual magneto-optical nanoprobe, endowed with properties useful for photodynamic therapy, has been prepared. It is constituted by a superparamagnetic iron oxide (SPIO) core (diameter size distribution centered at ca. 10 nm), obtained by thermal decomposition of iron oleate, coated by a compact silica shell, grown in a reverse microemulsion environment. Luminescent [Re(phen)(CO)3(py)]CF3SO3 complexes were covalently anchored to the silica shell, by functionalizing the pyridine ligand with a triethoxysilane moiety. Finally, the surface of the nanoparticles (NPs) was coated with a layer of polyethylene glycol (PEG), functionalized with triethoxysilane, to improve stability and stealthiness in physiological conditions. Transmission electron microscopy of these SPIO@SiO2-Re@PEG nanocomposites showed a single population, with size distribution centered at ca. 40 nm. NPs showed nuclear relaxivity values that guarantee an appreciable contrast in magnetic resonance imaging (r2 > 30 s-1 mM-1 at frequencies higher than 5 MHz). The presence of the Re complexes imparted photoluminescence to the NPs, with blue shifted emission and higher photoluminescence quantum yields with respect to the free [Re(phen)(CO)3(py-upts)]+ complex (λem 553 vs. 580 nm, Φ 0.060 vs. 0.038, in aerated water solution). The complexes embedded into the NPs maintained a satisfactory efficiency toward 1O2 generation (quantum yields 0.21 vs. 0.26 for the free complex, as assessed using 1,5-dihydroxynaphthalene as indirect marker of the 1O2 presence). Preliminary cell penetration tests were performed on human lung adenocarcinoma A549 cells. Two photon excitation confocal microscopy showed that the NPs were easily internalized and accumulated in the perinuclear region of the cells already after 4 h of incubation. Increased cytotoxicity upon irradiation with respect to the dark was also observed, showing the potential of the nanocomposite for photodynamic therapy applications.
- Galli, Marco,Moschini, Elisa,Dozzi, Maria Vittoria,Arosio, Paolo,Panigati, Monica,D'Alfonso, Laura,Mantecca, Paride,Lascialfari, Alessandro,D'Alfonso, Giuseppe,Maggioni, Daniela
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- An efficient multigram synthesis of juglone methyl ether
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Based on the regioselective oxidation of 1,4,5-trimethoxynaphthalene by cerium (IV) ammonium nitrate, an efficient synthesis of juglone methyl ether has been achieved with high overall yield (74%) and good purity (98.6%). Compared with the reported methods, the reaction conditions are milder and the work-up of each step is much simpler. Moreover, the new strategy considerably reduces the cost in the synthesis of juglone methyl ether and is suitable for large-scale preparations.
- Cui, Jia-Hua,Cui, Qing,Zhang, Qi-Jing,Li, Shao-Shun
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- Preparation and photo-oxidative functions of poly(ethylene-co-methacrylic acid) (PE-co-MAA) nanofibrous membrane supported porphyrins
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Surface functionalized poly(ethylene-co-methacrylic acid) (PE-co-MAA) nanofibrous membranes were successfully prepared and applied as solid supports to immobilize photosensitizers. Several activation agents were used to facilitate the surface functionalization of PE-co-MAA nanofibrous membranes, and PCl5 was found to be the most efficient one to activate surface carboxylic acid groups. Three spacers with variable lengths were introduced to the membrane surfaces prior to immobilizations of protoporphyrin IX (PPIX), a photosensitizer. The results revealed that the membranes with longer spacer chain incorporated more photoactive macrocyclic compounds, and the supported PPIX provided a more powerful catalytic effect on the photo-oxidation of 1,5-dihydroxynaphthalene. After five times of repeated catalytic reactions, the catalytic activity of the solid supported PPIX was maintained at 80% of the original power, and the membrane morphology was intact. The nanofibrous membrane supported photosensitizer provided high catalytic activity, easy handling, good durability and reusability. The Royal Society of Chemistry 2012.
- Zhu, Jing,Sun, Gang
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- Novel strategies for the synthesis of anthrapyran antibiotics: Discovery of a new antitumor agent and total synthesis of (S)-espicufolin
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Two high-yielding strategies for the synthesis of 4H-anthra[1,2-b]pyran antibiotics have been developed giving access to novel antitumor agent 24 (ED50 1.5 m) and to (S)-espicufolin (3). A key step for the assembly of the tetracyclic 4H-anthra[1,2-b]pyran-4,7,12-trione skeleton is the nucleophilic addition of an aryl lithium species onto an aldehyde which allows the introduction of either an ynone or 1,3-diketo side chain, serving as precursors for an acid-catalysed cyclisation. The Royal Society of Chemistry.
- Tietze, Lutz F.,Gericke, Kersten M.,Singidi, Ramakrishna Reddy,Schuberth, Ingrid
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- σ-Pt-BODIPY Complexes with Platinum Attachment to Carbon Atoms C2 or C3: Spectroscopic, Structural, and (Spectro)Electrochemical Studies and Photocatalysis
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In this work we discuss five new complexes with the general formula trans-Pt(bodipy)I(PEt3)2, where differently substituted bodipy dyes attach to the coordination center via a direct Pt-C σ-bond to the pyrrolic carbon atom C2 or C3. We also report an isolable intermediate of the oxidative addition step where the bodipy is 2-bonded to the cis-Pt(0)(PEt3)2 moiety. Comparison between the new complexes, meso-platinated analogue 8-Pt, and the parent dyes reveals that the site of platinum attachment influences the spectroscopic, photophysical, electrochemical, and electronic properties. In contrast to 8-Pt, absorption and emission bands are red-shifted with respect to the parent dyes. 2-Platinated bodipy dyes 2-Pt-6H, 2-Pt-6I, 2-Pt-Mes-6I, and 2-Pt-6Et exhibit dual fluorescence and NIR phosphorescence emissions, with low quantum yields, whereas 3-Pt emits solely by fluorescence (I:Fl = 52.7%). The complexes are modestly efficient sensitizers for photochemical 1O2 production but outperform methylene blue. They also undergo one reversible one-electron reduction and oxidation as indicated by cyclic voltammetry. Half-wave potentials are cathodically shifted by 340-510 mV with respect to the parent dyes. The one-electron reduced and some of the one-electron oxidized forms were generated and investigated by UV/vis/NIR and EPR spectroscopy as well as TD-DFT calculations. The similarity of their spectra to those of the one-electron reduced or oxidized forms of other bodipy dyes as well as the richly structured EPR spectra and g-values close to ge attest to a dominant bodipy character of the relevant frontier MOs.
- Irmler, Peter,Winter, Rainer F.
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- BODIPY-based photosensitizers with intense visible light harvesting ability and high 1O2 quantum yield in aqueous solution
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A novel method to enhance the singlet oxygen quantum yield of photosensitizers in aqueous solution has been developed by introducing an electron-withdrawing group into BODIPY. B-2 was prepared based on this method and shows intense light harvesting ability (ε = 6.8 × 104 M-1 cm-1 at 643 nm) and high 1O2 quantum yield in aqueous solution (Φ = 0.21). B-2 has been successfully used as an 1O2 sensitizer for the photo-oxidation of 1,5-dihydroxynaphthalene. This method substantially improves the photooxidation capability and photostability of 1O2 sensitizers in aqueous solution. This journal is
- Wu, Wenting,Geng, Ying,Fan, Weiyu,Li, Zhongtao,Zhan, Liying,Wu, Xueyan,Zheng, Jingtang,Zhao, Jianzhang,Wu, Mingbo
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- Oxidative Dearomatization of Phenols and Polycyclic Aromatics with Hydrogen Peroxide Triggered by Heterogeneous Sulfonic Acids
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We report herein a method for the oxidative dearomatization of phenols and bare polycyclic arenes into the corresponding quinoid derivatives using hydrogen peroxide. The reaction is catalyzed by sulfonic acids and best results were achieved using heterogenized species. The best results using phenols were achieved using a hybrid material, namely a perfluorinated polymer functionalized with sulfonic acid groups supported on silica. The dearomatization of polycyclic aromatic hydrocarbons performed better using the polymeric acid catalyst. These methods operate under mild conditions, using mild and benign oxidants and thus minimizing the formation of waste.
- Pancrazzi, Francesco,Maestri, Giovanni,Maggi, Raimondo,Viscardi, Rosanna
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supporting information
p. 5407 - 5414
(2021/10/25)
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- PHOTOOXIDATION OF PHENOLIC COMPOUNDS
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The present invention relates to the photooxidation of phenolic compounds to the respective quinoid compounds using methylene blue as photosensitizer in a solvent mixture of water and alcohols using light of the high wavelength range of the visible spectrum.
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Page/Page column 18
(2021/11/26)
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- Organophotocatalytic Aerobic Oxygenation of Phenols in a Visible-Light Continuous-Flow Photoreactor
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A mild photocatalytic phenol oxygenation enabled by a continuous-flow photoreactor using visible light and pressurized air is described herein. Products for wide-ranging applications, including the synthesis of vitamins, were obtained in high yields by precisely controlling principal process parameters. The reactor design permits low organophotocatalyst loadings to generate singlet oxygen. It is anticipated that the efficient aerobic phenol oxygenation to benzoquinones and p-quinols contributes to sustainable synthesis.
- Wellauer, Jo?l,Miladinov, Dragan,Buchholz, Thomas,Schütz, Jan,Stemmler, René T.,Medlock, Jonathan A.,Bonrath, Werner,Sparr, Christof
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supporting information
p. 9748 - 9752
(2021/05/27)
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- Synthesis, molecular docking, and biological activity of thioether derived from juglone in preclinical models of chronic myeloid leukemia
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In this work, 16 new thio-1,4-naphthoquinones were synthesized, and their antiproliferative effects against tumor cell lines SK-MEL-19, AGP-01, ACP-02, HL-60, K-562, K-562-Lucena-1, FEPS, and non-neoplastic human fibroblast MRC-5, were examined. The compounds were selective active against leukemia cell lines. Based on the screening results for cytotoxic activity, naphthoquinone 11a showed higher cytotoxicity on the chemoresistant leukemia (FEPS) cell line when compared to the chemosensitive (K-562) cell line. Moreover, naphthoquinone 11a presented excellent ADME/T and did not violate Lipinski's rule of five, indicating good oral absorption. Target prediction revealed DNA topoisomerase I (TOP1) as a possible target of 11a. The molecular docking prediction showed an ? 11.94 kcal/mol binding affinity interaction of 11a with TOP1, involving three hydrogen bonds to ARG364, A113, and G11 from the active site of the enzyme. In addition, naphthoquinone 11a significantly suppressed the expression of the TOP1 gene in K-562 and FEPS leukemia cell lines. The naphthoquinone 11a induced significant changes in cell morphology, demonstrating cell and nuclear shrinkage, blebbing formation as well and fragmentation of the cell into apoptotic bodies. Thus, 11a could be a drug that leads to a new set of TOP1 major inhibitors. In summary, the present study showed a cytotoxic effect of 11a against chemoresistant and chemosensitive leukemia cell lines with TOP1 as a possible target.
- B. S. M. R. Gomes, Carinne,Cordeiro, Pamella S.,Daniel, Julio P.,E. A. de Moraes, Maria,Ferreira, Vitor F.,Montenegro, Raquel C.,Moreira, Caroline S.,Vasconcellos, Marne C.,da Rocha, David R.,da S. M. Forezi, Luana,de F. A. Moreira-Nunes, Caroline,de S. Portilho, Adrhyann J.,do Nascimento, Vanessa
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- Synthetic Studies of the Rubellin Natural Products: Development of a Stereoselective Strategy and Total Synthesis of (+)-Rubellin C
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This manuscript describes our studies of the class of natural products known as the rubellins, culminating in the total synthesis of (+)-rubellin C. These anthraquinone-based natural products contain a variety of stereochemical and architectural motifs, including a 6-5-6-fused ring system, 5 stereogenic centers, and a central quaternary center. Herein, we report our development of a strategy to target the stereochemically dense core and anthraquinone nucleus, including approaches such as a bifunctional allylboron and vinyl triflate reagent, an anthraquinone benzylic metalation strategy, and a late-stage anthraquinone introduction strategy. Our studies culminate in a successful route to highly functionalized anthraquinone-based natural product scaffolds and a stereoselective total synthesis of (+)-rubellin C. These strategies and outcomes will aid in synthetic planning toward anthraquinone-based natural products of high interest.
- Gartman, Jackson A.,Tambar, Uttam K.
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p. 11237 - 11262
(2021/08/16)
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- Spatiotemporally controlled O2and singlet oxygen self-sufficient nanophotosensitizers enable the: In vivo high-yield synthesis of drugs and efficient hypoxic tumor therapy
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Carrying out the in vivo syntheses of drugs toxic to tumors based on the specific features of the tumor microenvironment is critical for ensuring specific antitumor efficacy. However, achieving in situ high-yield synthetic toxic drugs from non-toxic agents and reducing their drug resistance in hypoxic tumors remain challenges. Herein we created a tumor-microenvironment-responsive porous Pt/Pt(iv) methylene blue coordination polymer nanoshuttle (Pt/PtMBCPNS) photosensitizer with spatiotemporally controlled O2 and singlet oxygen (1O2) self-sufficient for the in vivo high-yield synthesis of drugs and efficient hypoxic tumor therapy. After being endocytosed, the nanophotosensitizer as a cascade catalyst was observed to effectively catalyze the conversion of endogenous H2O2 to O2, and was hence found to play a dual role in the enhanced tumor therapy. PtMBCPNSs, upon being irradiated with red light, efficiently converted O2 into 1O2. Subsequently, 1O2 oxidized non-toxic 1,5-dihydroxynaphthalene to form the anticancer agent juglone with a high yield. In addition, O2 was found to be able to improve the hypoxic microenvironment without light irradiation, thus enhancing the antitumor efficacy of the produced drugs and reducing drug resistance. As a result, by enhancing the synergistic effect of the treatment, this nanophotosensitizer significantly inhibited the growth of tumors and avoided damage to normal tissues/organs. Collectively, this work highlights a robust nanoplatform with the spatiotemporally controlled in vivo high-yield synthesis of drugs and generation of O2 to help overcome the current limitations of chemical-based therapies against hypoxic tumors.
- Chen, Fengjuan,Fu, Xu,Hai, Jun,He, Suisui,Li, Jieling,Li, Tianrong,Liang, Kun,Liu, Meilin,Liu, Sha,Lu, Siyu,Meng, Genping,Sun, Shihao,Wang, Baodui,Zhang, Lang
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p. 8817 - 8827
(2020/09/04)
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- Synthesis and biological evaluation of novel isothiazoloquinoline quinone analogues
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Natural quinones and their analogues have attracted growing attention because of their novel anticancer activities. A series of novel isothiazoloquinoline quinone analogues were synthesized and evaluated for antitumor activities against four different kind of cancer cells. Among them, isothiazoloquinolinoquinones inhibited cancer cells proliferation effectively with IC50 values in the nanomolar range, and isothiazoloquinolinoquinone 13a induced the cell apoptosis. Further exploration of possible mechanism of action indicates that 13a not only activates ROS production through NQO1-directed redox cycling but also inhibits the phosphorylation of STAT3. These findings indicate that 13a has potential use for the development of new skeleton drug candidate as an efficient substrate of NQO1 and STAT3 inhibitor.
- Chen, Ling,Gao, Jin-Lei,Hao, Ying,Kong, Fan-Rong,Liu, Hong-Dou,Liu, Li-Jun,Liu, Su-You,Luo, Zhi-Yong,Ma, Da-You,Wang, Liu-Liu,Xie, Yuan-Zhu,Zou, Zi-Zheng
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supporting information
(2020/06/22)
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- Anti-novel coronavirus naphthoquinone compound and medical application thereof
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The invention discloses an anti-novel coronavirus naphthoquinone compound and a medical application of the naphthoquinone compound. The structure of the compound is shown as a formula (I), wherein R1is hydrogen, methyl, ethyl, acetyl or propionyl; and R2 is hydrogen, methyl or ethyl. The compound disclosed by the invention has very strong activity of resisting the novel coronavirus, and can be used for inhibiting 3CL hydrolase (3C-like proteinase, 3CLpro) of the 2019-nCoV novel coronavirus. The in-vitro activity determination experiments show that the enzyme inhibition rate of part of the compounds reaches 99% under the concentration of 1 [mu] M. The naphthoquinone compound disclosed by the invention is clear in structure, simple and convenient in preparation method and high in yield, andhas important significance for developing efficient and low-toxicity novel anti-novel coronavirus drugs.
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(2020/06/20)
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- Oxidation of Electron-Rich Arenes Using HFIP-UHP System
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The straightforward oxidation of electron-rich arenes, namely, phenols, naphthols, and anisole derivatives, under mild reaction conditions, is described by means of the use of an environmentally benign HFIP-UHP system. The corresponding quinones or hydroxylated arenes were obtained in moderate to good yields.
- Llopis, Natalia,Baeza, Alejandro
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p. 6159 - 6164
(2020/05/20)
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- Doubly N-Confused Calix[6]phyrin Bis-Organopalladium Complexes: Photostable Triplet Sensitizers for Singlet Oxygen Generation
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Triplet photosensitizers that generate singlet oxygen efficiently are attractive for applications such as photodynamic therapy (PDT). Extending the absorption band to a near-infrared (NIR) region (700 nm≈) with reasonable photostability is one of the major demands in the rational design of such sensitizers. We herein prepared a series of mono- and bis-palladium complexes (1-Pd-H2, 2-Pd-H2, 1-Pd-Pd, and 2-Pd-Pd) based on modified calix[6]phyrins as photosensitizers for singlet oxygen generation. These palladium complexes showed intense absorption profiles in the visible-to-NIR region (500–750 nm) depending on the number of central metals. Upon photoirradiation in the presence of 1,5-dihydroxynaphthalene (DHN) as a substrate for reactive oxygen species, the bis-palladium complexes generated singlet oxygen with high efficiency and excellent photostability. Singlet oxygen generation was confirmed from the characteristic spectral feature of the spin trapped complex in the EPR spectrum and the intact 1O2 emission at 1270 nm.
- Pushpanandan, Poornenth,Won, Dong-Hoon,Mori, Shigeki,Yasutake, Yuhsuke,Fukatsu, Susumu,Ishida, Masatoshi,Furuta, Hiroyuki
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p. 1729 - 1736
(2019/01/29)
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- Perylenebisimide-fullerene dyads as heavy atom free triplet photosensitizers with unique singlet oxygen generation efficiencies
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We report the synthesis, characterization, photophysical and photochemical properties of two novel perylenebisimide-fullerene dyads (7 and 8) bearing one or two perylenebisimide (PBI) units as light harvester and a fullerene as spin converter. The molecular structures of all synthesized compounds were elucidated by elemental analyses, mass spectrometry, FT-IR, 1H and 13C NMR techniques. Their optical properties were investigated by UV–vis absorption and 2D/3D fluorescence emission spectroscopies. The photochemical studies via direct and indirect method endorsed PBI-fullerene dyads (7 and 8) as efficient heavy atom free tripletphotosensitizers whereas perylene derivatives did not exhibit any singlet oxygen production. The PBI-fullerene dyads exhibit excellent singlet oxygen quantum yields of 0.93 and 0.95. The PBI-fullerene dyads (7 and 8) are also able to use in the photooxidation of 1,5-dihydroxynaphtalene (DHN) to produce juglone and are recognized as stronger than MB as conventional triplet photosensitizers.
- ?ztürk, Ezel,Eserci, Hande,Okutan, Elif
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- Asymmetric synthesis of natural cis-dihydroarenediols using tetrahydroxynaphthalene reductase and its biosynthetic implications
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Asymmetric reduction of hydroxynaphthoquinones to secondary metabolites, (3S,4R)-3,4,8- A nd (2S,4R)-2,4,8-trihydroxy-1-tetralone, a putative biosynthetic diketo intermediate and a probable natural analogue, (3S,4R)-7-acetyl-3,4,8-trihydroxy-6-methyl-3,4-
- Saha, Nirmal,Müller, Michael,Husain, Syed Masood
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supporting information
p. 2204 - 2208
(2019/03/29)
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- Generation of Endocyclic Vinyl Carbene Complexes via Gold-Catalyzed Oxidative Cyclization of Terminal Diynes: Toward Naphthoquinones and Carbazolequinones
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Carbene cascade reactions involving carbene/alkyne metathesis have attracted much attention over the past decades because this chemistry offers great potential to build complicated cyclic molecules. However, the formed vinyl metal carbenoids in these reactions are limited to exocyclic carbenes, and the generation of endocyclic vinyl carbene complexes remains unexplored. Here, we report an unprecedented gold-catalyzed oxidative cyclization of terminal diynes. Importantly, the generation of endocyclic vinyl carbene complexes was involved in this oxidative cyclization, which is distinctively different from previous protocols. This method allows the facile synthesis of various valuable naphthoquinones and carbazolequinones from readily available diynes under exceptionally mild reaction conditions and features a broad substrate scope and wide functional group tolerance. Moreover, theoretical calculations provide further evidence on the divergent selectivity of this cyclization reaction.
- Shu, Chao,Shi, Chong-Yang,Sun, Qing,Zhou, Bo,Li, Tian-You,He, Qiao,Lu, Xin,Liu, Rai-Shung,Ye, Long-Wu
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p. 1019 - 1025
(2019/01/15)
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- The first solid state porphyrin-weak acid molecular complex: A novel metal free, nanosized and porous photocatalyst for large scale aerobic oxidations in water
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The first solid state porphyrin dication of a weak carboxylic acid was synthesized through the reaction of meso-tetrakis(N-methylpyridinium-4-yl)porphyrin (H2TMPyP) supported on the sodium salt of Amberlyst 15 nanoparticles (nanoAmbSO3/su
- Heydari-turkmani, Akram,Zakavi, Saeed
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p. 394 - 405
(2018/06/26)
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- Highly Efficient Synthesis and Structure–Activity Relationships of a Small Library of Substituted 1,4-Naphthoquinones
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A platform of highly efficient synthetic methodologies has been established to access a focused library of substituted 1,4-naphthoquinones derivatives functionalized with a diversity of amino/hydroxy/alkyl groups. Furthermore, the structure–activity relationship deduced from antiproliferative activities and toxicities of this 1,4-naphthoquinone library and intracellular reactive oxygen species (ROS) level detections might warrant future potential of plumbagin (2) and compound 13 as promising basic structures to develop novel anti-cancer agents.
- Bao, Na,Ou, Jinfeng,Shi, Wei,Li, Na,Chen, Li,Sun, Jianbo
-
supporting information
p. 2254 - 2258
(2018/06/04)
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- Functionalizing carbon nitride with heavy atom-free spin converters for enhanced 1O2 generation
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Carbon nitride as a metal-free conjugated polymer exhibits an intriguing prospect for the design of advanced photosensitizers for singlet oxygen (1O2) generation. However, the intersystem crossing (ISC) process is quite insufficient in carbon nitride, limiting the 1O2 generation. Here, we report a facile and general strategy to confined benzophenone as a heavy atom-free spin converter dopant in carbon nitride via the facile copolymerization. With proper energy level matching between the heavy atom-free spin converter and various ligands based on carbon nitride precursors, the proper combination can decrease the singlet-triplet energy gap (ΔEST) and hence generate 1O2 effectively. Due to its significant and selectivity for 1O2 generation, the as-prepared carbon nitride-based photosensitizer shows a high selective photooxidation activity for 1,5-dihydroxy-naphthalene (1,5-DHN). The product yield reached 71.8% after irradiation for 60 min, which was higher than that of cyclometalated PtII complexes (53.6%) in homogeneous photooxidation. This study can broaden the application of carbon nitride in the field of selective heterogeneous photooxidation due to simple operation, low cost, and high efficiency, making it a strong candidate for future industrialization.
- Wu, Wenting,Han, Congcong,Zhang, Qinhua,Zhang, Qinggang,Li, Zhongtao,Gosztola, David J.,Wiederrecht, Gary P.,Wu, Mingbo
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p. 222 - 229
(2018/04/02)
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- In vitro inhibition of Helicobacter pylori growth by redox cycling phenylaminojuglones
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Infection by Helicobacter pylori increases 10 times the risk of developing gastric cancer. Juglone, a natural occurring 1,4-naphthoquinone, prevents H. pylori growth by interfering with some of its critical metabolic pathways. Here, we report the design, synthesis, and in vitro evaluation of a series of juglone derivatives, namely, 2/3-phenylaminojuglones, as potential H. pylori growth inhibitors. Results show that 5 out of 12 phenylaminojuglones (at 1.5 μg/mL) were 1.5–2.2-fold more active than juglone. Interestingly, most of the phenylaminojuglones (10 out of 12) were 1.1–2.8 fold more active than metronidazole, a known H. pylori growth inhibitor. The most active compound, namely, 2-((3,4,5-trimethoxyphenyl)amino)-5-hydroxynaphthalene-1,4-dione 7, showed significant higher halo of growth inhibitions (HGI = 32.25 mm) to that of juglone and metronidazole (HGI = 14.50 and 11.67 mm). Structural activity relationships of the series suggest that the nature and location of the nitrogen substituents in the juglone scaffold, likely due in part to their redox potential, may influence the antibacterial activity of the series.
- Benites, Julio,Toledo, Héctor,Salas, Felipe,Guerrero, Angélica,Rios, David,Valderrama, Jaime A.,Buc Calderon, Pedro
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- Synthesis, spectroscopic studies and biological evaluation of acridine derivatives: The role of aggregation on the photodynamic efficiency
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Two new photoactive compounds (1 and 2) derived from the 9-amidoacridine chromophore have been synthesized and fully characterized. Their abilities to produce singlet oxygen upon irradiation have been compared. The synthesized compounds show very differen
- Felip-León, Carles,Martínez-Arroyo, Olga,Díaz-Oltra, Santiago,Miravet, Juan F.,Apostolova, Nadezda,Galindo, Francisco
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p. 869 - 874
(2018/02/21)
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- Ruthenium-catalyzed C-H oxygenation of quinones by weak O-coordination for potent trypanocidal agents
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Ruthenium-catalysis enabled the C-5 selective C-H oxygenation of naphthoquinones, and also sets the stage for the site-selective introduction of a hydroxyl group into anthraquinones. A-ring modified naphthoquinoidal compounds represent an important class of bioactive quinones for which the present study encompasses the first C-H oxygenation strategy by weak O-coordination.
- Dias, Gleiston G.,Rogge, Torben,Kuniyil, Rositha,Jacob, Claus,Menna-Barreto, Rubem F. S.,Da Silva Júnior, Eufranio N.,Ackermann, Lutz
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supporting information
p. 12840 - 12843
(2018/11/30)
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- New synthetic method of plumbagin
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The invention discloses a new synthetic method of plumbagin (PL), and relates to the technical field of medicine and chemical industry. The plumbagin becomes a study hot spot in treating rheumatoid arthritis and other domains. In recent years, literatures report that the plumbagin also has the effects of preventing bacterial and fungal and is used for the study of anticancer and anti-AIDS infection. However, the extraction rate of nature plumbagin is low, and the profit space is small; besides, the reported synthetic method of plumbagin is low in overall yield, high in cost, and not easy to acquire the raw material reagent, complex in post treatment process, and not friendly for environment; moreover, the purification process involves in column chromatography for many times. The raw material for the synthetic method of plumbagin is low in price and easy to acquire, and environment-friendly; the post treatment and purification process are simple, the yield is greatly promoted, the industrial production can be realized; meanwhile, the method provides an important reference basis for the subsequent scientific and research work.
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Paragraph 0032-0034
(2017/08/31)
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- Controlled Intercalation and Chemical Exfoliation of Layered Metal-Organic Frameworks Using a Chemically Labile Intercalating Agent
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Creating ordered two-dimensional (2D) metal-organic framework (MOF) nanosheets has attracted extensive interest. However, it still remains a great challenge to synthesize ultrathin 2D MOF nanosheets with controlled thickness in high yields. In this work, we demonstrate a novel intercalation and chemical exfoliation approach to obtain MOF nanosheets from intrinsically layered MOF crystals. This approach involves two steps: first, layered porphyrinic MOF crystals are intercalated with 4,4′-dipyridyl disulfide through coordination bonding with the metal nodes; subsequently, selective cleavage of the disulfide bond induces exfoliation of the intercalated MOF crystals, leading to individual freestanding MOF nanosheets. This chemical exfoliation process can proceed efficiently at room temperature to produce ultrathin (~1 nm) 2D MOF nanosheets in ~57% overall yield. The obtained ultrathin nanosheets exhibit efficient and far superior heterogeneous photocatalysis performance compared with the corresponding bulk MOF.
- Ding, Yanjun,Chen, Ying-Pin,Zhang, Xinlei,Chen, Liang,Dong, Zhaohui,Jiang, Hai-Long,Xu, Hangxun,Zhou, Hong-Cai
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p. 9136 - 9139
(2017/07/22)
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- Bright, Multi-responsive, Sky-Blue Platinum(II) Phosphors Based on a Tetradentate Chelating Framework
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A new class of highly efficient and stable, blue-phosphorescent PtII complexes based on a tetradentate chelating framework has been found to exhibit highly sensitive and reversible responses to multiple external stimuli including temperature, pressure, and UV irradiation with distinct phosphorescent color switching—from blue to red or white. Intermolecular excimer formation is the main origin of this intriguing multi-response phenomenon. Highly efficient singlet-oxygen sensitization by the PtII compounds yields UV-light-induced phosphorescence enhancement and color switching.
- Liu, Lijie,Wang, Xiang,Wang, Nan,Peng, Tai,Wang, Suning
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supporting information
p. 9160 - 9164
(2017/07/25)
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- Method for synthesizing naphthoquinone compounds by photocatalytic oxidation of naphthol compounds
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The invention discloses a method for synthesizing naphthoquinone compounds by photocatalytic oxidation of naphthol compounds, comprising the steps of dissolving the naphthol compounds in a mixed solution of isopropanol and water to obtain a reaction liqui
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Paragraph 0038
(2017/05/10)
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- Exploiting photooxygenations mediated by porphyrinoid photocatalysts under continuous flow conditions
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Photooxygenation reactions are a powerful synthetic tool to produce oxidized organic compounds; however, these reactions often exhibit experimental limitations including the production of complex mixtures that hinder desired product isolation and scale-up. Herein, we present a photocatalysed protocol under continuous flow conditions using a simple home built photoreactor and porphyrinoids as photocatalysts. Reaction conditions, long-term experiments, and scope demonstrate a protocol that is cost-effective, safe, reproducible and robust, thus allowing the production of relevant substituted naphthoquinones with interest in natural product synthesis and biological activity.
- De Oliveira, Kleber T.,Miller, L. Zane,McQuade, D. Tyler
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p. 12717 - 12725
(2016/02/12)
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- Synthesis, properties and singlet oxygen generation of thiazolidinone double bond linked porphyrin at meso and β-position
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Meso and β-substituted free base and zinc metallated thiazolidinone-porphyrin conjugates were synthesized by one pot four component Knoevenagel condensation by utilizing substituted amines, carbon disulfide, ethyl chloroacetate and porphyrin aldehydes. These newly synthesized conjugates were characterized by IR, 1H NMR, 13C NMR, UV-Vis, fluorescence and HRMS spectroscopy. The singlet oxygen generation behaviors of these porphyrin conjugates were studied and it was observed that these porphyrin conjugates followed type II singlet oxygen. Fluorescence and singlet oxygen quantum yields among meso-substituted (mono-, di, tetra) and β-substituted conjugates were examined. The photocatalytic photooxidation of naphthols and furan by using these new organic photocatalysts were further analysed and it was observed that meso-tetra substituted (Zn3a) and β-substituted (Zn6a) porphyrins are much efficient for generation of singlet oxygen and for photocatalytic photooxidation.
- Ahmad, Sohail,Yadav, Kumar Karitkey,Narang, Uma,Bhattacharya, Soumee,Singh, Sarangthem Joychandra,Chauhan
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p. 36090 - 36095
(2016/05/19)
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- Synthesis of covalently bonded boron-dipyrromethene-diarylethene for building a stable photosensitizer with photo-controlled reversibility
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We report the synthesis and characterization of a photosensitizer containing boron-dipyrromethene and diarylethene. The photosensitizer has photo-controlled reversible photosensitivity and offers potential applications in photochemical catalysis and the d
- Hu, Qiao-Ju,Lu, Yu-Chen,Yang, Cheng-Xiong,Yan, Xiu-Ping
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p. 5470 - 5473
(2016/05/09)
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- Complexes: Trans -Pt(BODIPY)X(PEt3)2: Excitation energy-dependent fluorescence and phosphorescence emissions, oxygen sensing and photocatalysis
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We report on five new complexes with the general formula trans-Pt(BODIPY)X(PEt3)2 (Pt-X), where the platinum(ii) ion is σ-bonded to a 4,4-difluoro-4-bora-3a,4a-diaza-s-indacen-8-yl (BODIPY) and an anionic ligand X- (X- = Cl-, I-, NO2-, NCS-, CH3-). All five complexes were characterized by multinuclear NMR, electronic absorption and luminescence spectroscopy and by X-ray diffraction analysis. Four of these complexes show efficient intersystem crossing (ISC) from an excited singlet state to a BODIPY-centred T1 state and exhibit dual fluorescence and phosphorescence emission from the BODIPY ligand. In Pt-I, the fluorescence is almost completely quenched, whereas the phosphorescence quantum yield reaches a value of 40%. The rate of ISC and the ratio of phosphorescence to fluorescence emissions depend on the excitation wavelength (i.e. on which specific transition is excited). The performance of these complexes as one-component oxygen sensors and their photocatalytic activities were tested by Stern-Volmer quenching experiments and by monitoring the oxidation of 1,5-dihydroxynaphthalene with 1O2 generated from the long-lived triplet state of the sensitizer by triplet-triplet annihilation with 3O2. Exceptionally high 1O2 generation quantum yields of up to near unity were obtained.
- Irmler, Peter,Winter, Rainer F.
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p. 10420 - 10434
(2016/07/11)
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- Sequential, One-Pot Access to Arylated Benzoquinones/Naphthoquinones from Phenols/Naphthols
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A sequential one-pot approach towards arylated benzoquinones and naphthoquinones is reported. The reaction proceeds through oxidation of phenols/naphthols followed by CH-arylation with a catalytic amount of triflic acid. Preliminary cytotoxic studies were carried out with five different cell lines and some of the compounds show promising activity. This one-pot approach towards arylated benzoquinones and naphthoquinones proceeds through oxidation of phenols/naphthols followed by CH-arylation. Preliminary cytotoxic studies for some of the compounds showed promising activity.
- Jiang, Jia-Heng,Boominathan, Siva Senthil Kumar,Hu, Wan-Ping,Chen, Chung-Yu,Vandavasi, Jaya Kishore,Lin, Ying-Ting,Wang, Jeh-Jeng
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p. 2284 - 2289
(2016/05/19)
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- Synthesis and biological evaluation of lipophilic 1,4-naphthoquinone derivatives against human cancer cell lines
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To examine the effect of hydrophobicity on the anticancer activity of 1,4-naphthoquinone derivatives, a series of compounds bearing a 2-O-alkyl-, 3-C-alkyl- or 2/3-N-morpholinoalkyl group were synthesized and evaluated for their anticancer activity against five human cancer cell lines in vitro. The cytotoxicity of these derivatives was assayed against HT-29, SW480, HepG2, MCF-7 and HL-60 cells by the MTT assay. Among them, 2-hydroxy-3-farnesyl-1,4-naphthoquinone (11a) was found to be the most cytotoxic against these cell lines. Our results showed that the effectiveness of compound 11a may be attributed to its suppression of the survival of HT-29. Secondly, in the Hoechst 33258 staining test, compound 11a-treated cells exhibited nuclear condensation typical of apoptosis. Additionally, cell cycle analysis by flow cytometry indicated that compound 11a arrested HT-29 cells in the S phase. Furthermore, cell death detected by Annexin V-FITC/propidium iodide staining showed that compound 11a efficiently induced apoptosis of HT-29 in a concentration-dependent manner. Taken together, compound 11a effectively inhibits colon cancer cell proliferation and may be a potent anticancer agent.
- Wang, Shao-Hung,Lo, Chih-Yu,Gwo, Zhong-Heng,Lin, Hong-Jhih,Chen, Lih-Geeng,Kuo, Cheng-Deng,Wu, Jin-Yi
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p. 11994 - 12015
(2015/08/18)
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- 1,2-Naphthoquinone-based Derivatives and and Methods for Preparing them
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The present invention relates to a compound represented by chemical formula (1), a pharmaceutically acceptable salt, a hydrate, a solvate, a prodrug, a tautomer, an enantiomer, or a pharmaceutically acceptable diastereomer thereof, a preparing method thereof, and a medical composition having a treating or preventing effect of metabolic diseases containing the same. Here, R_1 to R_3, and X_1 to X_6 are the same as defined in a first claim.COPYRIGHT KIPO 2015
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Paragraph 0300-0303
(2016/11/24)
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- Photochromic metal-organic frameworks: Reversible control of singlet oxygen generation
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(Figure Presented). The controlled generation of singlet oxygen is of great interest owing to its potential applications including industrial wastewater treatment, photochemistry, and photodynamic therapy. Two photochromic metal-organic frameworks, PC-PCN and SO-PCN, have been developed. A photochromic reaction has been successfully realized in PC-PCN while maintaining its single crystallinity. In particular, as a solid-state material which inherently integrates the photochromic switch and photosensitizer, SO-PCN has demonstrated reversible control of 1O2 generation. Additionally, SO-PCN shows catalytic activity towards photooxidation of 1,5-dihydroxynaphthalene.
- Park, Jihye,Feng, Dawei,Yuan, Shuai,Zhou, Hong-Cai
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supporting information
p. 430 - 435
(2015/02/19)
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- The ionic liquid and having a similar structure catalyst photooxidative porphysen compd.
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PROBLEM TO BE SOLVED: To provide a porphycene compound having an ionic liquid-like structure, usable in a homogeneous system and also easily reusable, and a photooxidation catalyst containing the same compound. SOLUTION: This porphycene compound expressed by formula (1) [wherein, R1to R12are each independently H, a halogen atom, nitro, cyano, sulfone, 1-10C alkyl, 3-6C cycloalkyl, 1-6C alkoxy, phenyl or -SO2-NH-(CH2)n-AX (wherein, n is an integer of 1 to 20; A is a cation containing a quaternary nitrogen atom; and X is a counter anion); provided that at least one of the R1to R12is the -SO2-NH-(CH2)n-AX (wherein, the n, A and X are each same meaning as above)], and the photooxidation catalyst containing the same are provided. COPYRIGHT: (C)2011,JPO&INPIT
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Paragraph 0032; 0035
(2016/11/07)
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- An efficient synthesis of 5, 6-dimethoxy 1- and 2-naphthols via Teuber reaction
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Based on the oxidation of 1, 5-naphthalenediol (4) and 6-bromo-2-naphthol (9) via Teuber reaction, an efficient synthesis of 5, 6-dimethoxy-1-naphthol (1) and 5, 6-dimethoxy-2-naphthol (2) was achieved with high overall yield (16% for 1 and 25% for 2). The key steps of the synthetic strategy involved the oxidation of naphthols (4 and 9) to the corresponding naphthoquinones (5 and 10) and the conversion of 5, 6-dimethoxy- 2-naphthaldehyde to 5, 6-dimethoxy-2-naphthol formate through Baeyer-Villiger oxidation-rearrangement.
- Cui, Jia-Hua,Li, Shao-Shun
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p. 1163 - 1168
(2013/10/22)
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- Intramolecular RET enhanced visible light-absorbing bodipy organic triplet photosensitizers and application in photooxidation and triplet-triplet annihilation upconversion
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Resonance energy transfer (RET) was used for the first time to enhance the visible light absorption of triplet photosensitizers. The intramolecular energy donor (boron-dipyrromethene, Bodipy) and acceptor (iodo-Bodipy) show different absorption bands in v
- Zhang, Caishun,Zhao, Jianzhang,Wu, Shuo,Wang, Zilong,Wu, Wanhua,Ma, Jie,Guo, Song,Huang, Ling
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supporting information
p. 10566 - 10578
(2013/08/23)
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- Observation of the long-lived triplet excited state of perylenebisimide (PBI) in C^N cyclometalated Ir(iii) complexes and application in photocatalytic oxidation
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Perylenebisimide (PBI) was used to prepare CN cyclometalated Ir(iii) complexes that show strong absorption of visible light and it is the first time the long-lived triplet excited state of PBI chromophore was observed in a transition metal complex (τT = 22.3 μs). Previously, the lifetime of the triplet state of PBI in transition metal complexes was usually shorter than 1.0 μs. Long-lived triplet excited states are useful for applications in photocatalysis or other photophysical processes concerning triplet-triplet-energy-transfer. PBI and amino-PBI were used for preparation of cyclometalated Ir(iii) complexes (Ir-2 and Ir-3), in which the PBI chromophore was connected to the coordination center via CC π-conjugation bond. The new complexes show strong absorption in visible region (ε = 34200 M -1 cm-1 at 541 nm for Ir-2, and ε = 19000 at 669 nm for Ir-3), compared to the model complex Ir(ppy)(bpy)[PF6] Ir-1 (ε -1 cm-1 in the region beyond 400 nm). The nanosecond time-resolved transient absorption and DFT calculations indicated that PBI-localized long-lived 3IL states were populated for Ir-2 and Ir-3 upon photoexcitation. The complexes were used as triplet photosensitizers for 1O2-mediated photooxidation of 1,5-dihydronaphthalene to produce juglone, an important intermediate for preparation of anti-cancer compounds. 1O2 quantum yields (ΦΔ) up to 91% were observed for the new Ir(iii) complexes and the overall photosensitizing ability is much higher than the conventional Ir(iii) complex Ir-1, which shows the typical weak visible light absorption in visible region. Our results are useful for preparation of transition metal complexes that show strong absorption of visible light and long-lived triplet excited state and for the application of these complexes in photocatalysis. The Royal Society of Chemistry 2013.
- Sun, Jifu,Zhong, Fangfang,Zhao, Jianzhang
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p. 9595 - 9605
(2013/08/23)
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- Efficient enhancement of the visible-light absorption of cyclometalated Ir(III) complexes triplet photosensitizers with bodipy and applications in photooxidation and triplet-triplet annihilation upconversion
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We report molecular designing strategies to enhance the effective visible-light absorption of cyclometalated Ir(III) complexes. Cationic cyclometalated Ir(III) complexes were prepared in which boron-dipyrromethene (Bodipy) units were attached to the 2,2′-
- Sun, Jifu,Zhong, Fangfang,Yi, Xiuyu,Zhao, Jianzhang
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p. 6299 - 6310
(2013/07/11)
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- Activated zeolites and heteropolyacids: An efficient catalysts for the synthesis of triacetoxyaromatic precursors of hydroxyquinones
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The Thiele-Winter reaction is of interest for synthesis of triacetoxyaromatic precursors of hydroquinones. Liquid acid such as, chlorosulfonic acid and solid acids like heteropolyacids have an efficient catalyst can effectively replace sulfuric acid in acetoxylation reaction of quinones without use of organic solvent at room temperature.
- Hadjila, Dokari,Mohamed, Hammadi
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p. 6112 - 6116
(2013/07/26)
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- Bodipy derivatives as organic triplet photosensitizers for aerobic photoorganocatalytic oxidative coupling of amines and photooxidation of dihydroxylnaphthalenes
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We used iodo-Bodipy derivatives that show strong absorption of visible light and long-lived triplet excited states as organic catalysts for photoredox catalytic organic reactions. Conventionally most of the photocatalysts are based on the off-the-shelf compounds, usually showing weak absorption in the visible region and short triplet excited state lifetimes. Herein, the organic catalysts are used for two photocatalyzed reactions mediated by singlet oxygen ( 1O2), that is, the aerobic oxidative coupling of amines and the photooxidation of dihydroxylnaphthalenes, which is coupled to the subsequent addition of amines to the naphthoquinones, via C-H functionalization of 1,4-naphthoquinone, to produce N-aryl-2-amino-1,4-naphthoquinones (one-pot reaction), which are anticancer and antibiotic reagents. The photoreactions were substantially accelerated with these new iodo-Bodipy organic photocatalysts compared to that catalyzed with the conventional Ru(II)/Ir(III) complexes, which show weak absorption in the visible region and short-lived triplet excited states. Our results will inspire the design and application of new organic triplet photosensitizers that show strong absorption of visible light and long-lived triplet excited state and the application of these catalysts in photoredox catalytic organic reactions.
- Huang, Ling,Zhao, Jianzhang,Guo, Song,Zhang, Caishun,Ma, Jie
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p. 5627 - 5637
(2013/07/25)
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