- Synthesis of perinaphthenones through rhodium-catalyzed dehydrative annulation of 1-naphthoic acids with alkynes
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An efficient approach to the synthesis of perinaphthenones via the rhodium-catalyzed dehydrative annulation of 1-naphthoic acids with internal alkynes was developed. Norbornadiene can act as an acetylene equivalent to give unsubstituted perinaphthenones at the 2- and 3-positions via dehydrative annulation followed by a retro Diels-Alder reaction.
- Fukuyama, Takahide,Sugimori, Taiki,Maetani, Shinji,Ryu, Ilhyong
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- 4-Hydroxyl-oxoisoaporphine, one small molecule as theranostic agent for simultaneous fluorescence imaging and photodynamic therapy as type II photosensitizer
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Oxoisoaporphine (OA) is a plant phototoxin isolated from Menispermaceae, however, its weak fluorescence and low water solubility impede it for theranostics. We developed here 4-hydroxyl-oxoisoaporphine (OHOA), which has good singlet oxygen-generating ability (0.06), strong fluorescence (0.72) and improved water solubility. OHOA displays excellent fluorescence for cell imaging and exhibits light-induced cytotoxicity against cancer cell. In vitro model of human cervical carcinoma (HeLa) cell proved that singlet oxygen generated by OHOA triggered photosensitized oxidation reactions and exert toxic effect on tumor cells. The MTT assay using HeLa cells verified the low cytotoxicity of OHOA in the dark and high phototoxicity. Confocal experiment indicates that OHOA mainly distributes in mitochondria and western blotting demonstrated that OHOA induces cell apoptosis via the mitochondrial pathway in the presence of light. Our molecule provides an alternative choice as a theranostic agent against cancer cells which usually are in conflict with each other for most traditional theranostic agents. Graphic abstract: [Figure not available: see fulltext.]
- Xu, Qi,Ji, Yunfan,Chen, Meijun,Shao, Xusheng
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- Synthesis and insecticidal evaluation of phytoalexin phenalenones derivatives
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Phenalenone is a kind of defensive compound biosynthesized inside plants in response to the outside attack such as fungus and nematodes. A set of derivatives encompassing structural modifications on the privileged phenalenone scaffold were synthesized through introduction of phenyl and hydroxyl substitutes at 9-positon and 2-position and assessed their insecticidal activities against armyworm (Mythimna separata Walker) and cowpea aphids (Aphis craccivora). No obvious insecticidal activities of the synthesized compounds were observed against armyworm. Some of the 9-phenyl and 2-hydroxy substituted phenalenone analogues showed potential activities against cowpea aphids with 33%–41% mortality at 500?mg/L.
- Zhang, Ya-Nan,Feng, Yi-An,Li, Zhong,Shao, Xu-Sheng
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- Measuring human carboxylesterase 2 activity in pancreatic cancer patient-derived xenografts using a ratiometric fluorescent chemosensor
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Irinotecan-based therapy is a common treatment for pancreatic cancer. To elicit its anticancer activity, the drug requires first the hydrolysis action of the enzyme human carboxylesterase 2 (hCES2). It has been established that pancreatic cancer patients have various levels of hCES2, whereby patients having low levels respond poorer to Irinotecan than patients with higher levels, suggesting that hCES2 can be used to predict response. However, current methods that measure hCES2 activity are inaccurate, complex or lengthy, thus being incompatible for use in a clinical setting. Here, we developed a small molecule ratiometric fluorescent chemosensor that accurately measures hCES2 activity in a single-step within complex mixtures. Our chemosensor is highly selective for hCES2 over hCES1, cell permeable and can measure hCES2 activity in pancreatic cancer patient-derived xenografts. Given the simplicity, accuracy and tissue compatibility of our assay, we anticipate our chemosensor can be used to predict patient response to Irinotecan-based therapy.
- Kailass, Karishma,Sadovski, Oleg,Capello, Michela,Kang, Ya'an,Fleming, Jason B.,Hanash, Samir M.,Beharry, Andrew A.
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- Light-induced activities of novel naphtho[1,8-ef]isoindole-7,8,10(9H)-trione and oxoisoaporphine derivatives towards mosquito larvae
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Infected mosquitoes are significant vectors of dengue, yellow fever, chikungunya, zika and other pathogens. In the view of increasing resistance in mosquito larvae control, photoactivated insecticides is a promising approach by utilizing highly toxic singlet oxygen produced by photosensitizer through irradiation. However, the choice of photosensitizer for mosquito control is limited. Here, we report a novel series of naphtho[1,8-ef]isoindole-7,8,10(9H)-trione and oxoisoaporphines derivatives as excellent type II photosensitizers. Meanwhile, the light-dependent activities against permethrin-susceptible and permethrin-resistant strain of Aedes aegypti mosquito larvae of these compounds were evaluated. Among them, compound 7b was proved to be potential photodynamic insecticide due to its excellent phototoxicity, the LC50 value was 0.19 μg mL?1 under visible light irradiation. The irradiation-generated enhancement in the activity was more than 520-fold. This compound could be the potential candidate in the search for new photoactivated insecticide leads. Importantly, 7b has good fluorescence quantum yield (?F = 0.70), it can be used as a fluorescence indicator in mosquito larvae to observe uptake and morphology change.
- Feng, Hao,Shao, Xusheng,Xu, Qi
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supporting information
(2021/07/14)
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- A Green-Absorbing, Red-Fluorescent Phenalenone-Based Photosensitizer as a Theranostic Agent for Photodynamic Therapy
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Phenalenone is a synthetically accessible, highly efficient photosensitizer with a near-unity singlet oxygen quantum yield. Unfortunately, its UV absorption and lack of fluorescence has made it unsuitable for fluorescence-guided photodynamic therapy against cancer. In this work, we synthesized a series of phenalenone derivatives containing electron-donating groups to red-shift the absorption spectrum and bromine(s) to permit good singlet oxygen production via the heavy-atom effect. Of the derivatives synthesized, the phenalenone containing an amine at the 6-position with bromines at the 2- and 5-positions (OE19) exhibited the longest absorption wavelength (i.e., green) and produced both singlet oxygen and red fluorescence efficiently. OE19 induced photocytotoxicity with nanomolar potency in 2D cultured PANC-1 cancer cells as well as light-induced destruction of PANC-1 spheroids with minimal dark toxicity. Overall, OE19 opens up the possibility of employing phenalenone-based photosensitizers as theranostic agents for photodynamic cancer therapy.
- Kaye, Esther G.,Kailass, Karishma,Sadovski, Oleg,Beharry, Andrew A.
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supporting information
p. 1295 - 1301
(2021/08/01)
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- Concise Synthesis of Natural Phenylphenalenone Phytoalexins and a Regioisomer
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Concise total syntheses of the natural phytoalexins 2-hydroxy-8-(4-hydroxyphenyl)phenalen-1-one (1), 2-hydroxy-8-(3,4-dihydroxyphenyl)phenalen-1-one (2), and hydroxyanigorufone (4), together with regioisomer 3 are accomplished in 11 or 12 steps. The synthetic strategy features a Friedel-Crafts acylation to construct the 1H-phenalen-1-one tricyclic core followed by a Suzuki cross-coupling to obtain the target compounds.
- Wang, Ming-Zhong,Ku, Chuen-Fai,Si, Tong-Xu,Tsang, Siu-Wai,Lv, Xiao-Meng,Li, Xiao-Wan,Li, Zheng-Ming,Zhang, Hong-Jie,Chan, Albert S. C.
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- Synthesis of Positional Isomeric Phenylphenalenones
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A series of isomeric phenylphenalenones in which the phenyl ring is located at all possible peripheral positions of the phenalenone nuclei was synthesized. The structural characteristics of the series, in which topological variation is permitted with minimal electronic disturbance, could, in principle, allow for easy pharmacophore recognition when the compounds are aligned in steroidomimetic conformations.
- Ospina, Felipe,Ramirez, Adrian,Cano, Marisol,Hidalgo, William,Schneider, Bernd,Otálvaro, Felipe
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p. 3873 - 3879
(2017/04/11)
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- Improving photodynamic inactivation of bacteria in dentistry: Highly effective and fast killing of oral key pathogens with novel tooth-colored type-II photosensitizers
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Increasing antibiotic resistances in microorganisms create serious problems in public health. This demands alternative approaches for killing pathogens to supplement standard treatment methods. Photodynamic inactivation of bacteria (PIB) uses light activated photosensitizers (PS) to generate reactive oxygen species immediately upon illumination, inducing lethal phototoxicity. Positively charged phenalen-1-one derivatives are a new generation of PS for light-mediated killing of pathogens with outstanding singlet oxygen quantum yield ΦΔ of >97%. Upon irradiation with a standard photopolymerizer light (bluephase C8, 1260 ± 50 mW/cm2) the PS showed high activity against the oral key pathogens Enterococcus faecalis, Actinomyces naeslundii, Streptococcus mutans, and Aggregatibacter actinomycetemcomitans. At a concentration of 10 μM, a maximum efficacy of more than 6 log10 steps (≥99.9999%) of bacteria killing is reached in less than 1 min (light dose 50 J/cm2) after one single treatment. The pyridinium substituent as positively charged moiety is especially advantageous for antimicrobial action.
- Sp?th, Andreas,Leibl, Christoph,Cieplik, Fabian,Lehner, Karin,Regensburger, Johannes,Hiller, Karl-Anton,B?umler, Wolfgang,Schmalz, Gottfried,Maisch, Tim
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p. 5157 - 5168
(2014/07/08)
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- Diversity-oriented synthesis leads to an effective class of bifunctional linchpins uniting anion relay chemistry (ARC) with benzyne reactivity
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In conjunction with the construction of a diversity-oriented synthesis library of 10-membered ring "natural product-like" macrolides, the design, synthesis, and validation of a unique class of bifunctional linchpins, uniting benzyne reactivity initiated by type II anion relay chemistry (ARC) has been achieved, permitting access to diverse [2+2], [3+2], and [4+2] cycloadducts.
- Smith III, Amos B.,Kim, Won-Suk
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p. 6787 - 6792
(2012/03/26)
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- A New method of synthesizing phenalen-1-one: Reduction of 3-hydroxyphenalen-1-one using nabh4 and lanthanoid chlorides
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Phenalen-1-one was obtained in considerable yield by reducing 3-hydroxyphenalen-1-one. Most of known preparation methods are not very practical, either because their yields are very poor or because their processes have many steps. This regioselective 1,2-reduction proceeded by the action of NaBH4 and various cations of rare-earth elements and metals. The yields of phenalen-1-one were examined as a function of typical lanthanoids, molar ratios of lanthanoid ions to 3-acetoxy-phenalen-1-one, and differing methods of protecting the hydroxyl group. Lanthanum chloride (LaCl3) gave the greatest yield (45.3%) of phenalen-1-one at molar ratios higher than a third, probably because La3+ ion is a hard acid and coordinates easily to a hard solvent such as methanol. Further, it has the largest ionic radius among all lanthanoid ions. Copyright Taylor & Francis Group, LLC.
- Sawada, Tadanobu,Ishii, Hiroyuki,Ueda, Toyotoshi,Aoki, Junji
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experimental part
p. 3912 - 3923
(2009/12/08)
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- Evolution of products in the combustion of scrap tires in a horizontal, laboratory scale reactor
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A horizontal laboratory reactor was used to study the evolution of byproducts from the combustion of scrap tires at five nominal temperatures (ranging from 650 to 1050 °C) and different oxygen:sample ratios A model was used to calculate the bulk air ratio (λ), and the oxygen consumption was discussed considering this ratio λ. More than 100 volatile and semivolatile compounds were identified and quantified by gas chromatography mass spectrometry, plotting their yields vs the bulk air ratio and temperature. Five different behaviors considering the bulk air ratio and the temperature were identified.
- Fullana,Font,Conesa,Blasco
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p. 2092 - 2099
(2007/10/03)
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- Synthetic approaches to the hypothetical lactone intermediate in the pyrolytic conversion of 8-methylcyclobuta[a]naphthalene-1,2-dione into acenaphthylene
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Synthetic approaches to the hypothetical lactone intermediate 8,8a-dihydro-2H-acenaphtho[1,8-bc]furan-2-one (2) based on intramolcular Diels-Alder reaction, and on intramolecular alkylation by diazoacetate groups, were not useful. Generation and pyrolysis of the 9-diazomethylnaphtho[1,2-c]furan-3(1H)-one (19) derived from the corresponding 9-formyl compound (15) gave products including acenaphthylene, consistent with the intermediacy of the lactone (2).
- Brown, Roger F.C.,Eastwood, Frank W.,Wong, Neil R.
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p. 793 - 800
(2007/10/03)
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- THE BEHAVIOR OF THE SINGLET AND TRIPLET SPIN STATES OF METHYLENE-BRIDGED 1,8-NAPHTHOQUINODIMETHANE WITH O2
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It has been shown that thermolysis of naphthocyclopropane 8 yields the singlet 1,8-naphthoquinodimethane 7 by disrotatory ring opening.In fluid solution the singlet biradical prefers to ring close to regenerate the starting material rather than under a 1,2-hydrogen shift to yield phenalene (9).It has been demonstrated that the singlet 7 does not react with O2 or undergo intersystem crossing to ground state triplet 7.It has also been shown by an intricate set of experiments that triplet 7 is produced on photolysis of 8 and that it reacts with O2.Unfortunately, it was not possible to elucidate unequivocally the mechanism by which triplet 7 reacts with O2.
- Pagni, Richard M.,Burnett, Michael N,,Hassaneen,Hamdi M.
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p. 843 - 851
(2007/10/02)
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- PHOTOLYSIS OF 6-SUBSTITUTED PHENALENONES IN DEAERATED ALCOHOL MEDIA
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The photolysis of phenalenone and its derivatives containing the substituents NH2, NHCH3, N(CH3)2, NHC2H4OH, NHCH2C6H5, O-, OCH3, Cl at position 6 in ethanol leads to photodehydrogenation of the alcohol.The effectiveness of the process depends significantly on the nature of the substituent.The relationship between the quantum yield of the photodehydrogenation and the intensity of the light flux, the energy of the quanta, and the concentration of the substrate were determined.The possibility of sensitization of the process was demonstrated.The mechanism of photodehydrogenation is discussed.
- Kuznetsova, N. A.,Reznichenko, A. V.,Kokin, V. N.,Kaliya, O. L.
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p. 540 - 544
(2007/10/02)
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- TRANSFORMATIONS OF POLYCYCLIC KETONES. XVII. SYNTHESIS OF 3-AMINO-1-PHENALENONE AND ITS SUBSTITUTED DERIVATIVES
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The action of ammonia and primary amines on 1,3-phenalenedione under mild conditions leads to the ready formation of 3-amino-1-phenalenone and its N-alkyl and N-aryl derivatives.Unlike 2-, 5-, and 6-amino-1-phenalenones, 3-amino-1-phenalenone does not form a diazo compound in reaction with sodium nitrite, and this demonstrates its similarity to β-aminovinylcarbonyl compounds.
- Solodar', S. L.,Kochkin, V. A.
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p. 1809 - 1812
(2007/10/02)
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