RESUMO
To circumvent the adverse impacts arising from an excessive use of fossil fuels, bioenergy and chemical production from a carbon neutral resource (biomass) has drawn considerable attention over the last two decades. Among various technical candidates, fast pyrolysis of biomass has been considered as one of the viable technical routes for converting a carbonaceous material (biomass) into biocrude (bio-oil). In these respects, three biomass samples (i.e., sawdust, empty fruit bunch, and giant Miscanthus) were chosen as a carbon substrate for the pyrolysis process in this study. A pilot-scale circulating fluidized bed reactor was employed for the pyrolysis work, and biocrude from the fast pyrolysis process at 500⯰C were characterized because the maximum yield of biocrude (60â¯wt% of the original sample mass) was achieved at 500⯰C. The physico-chemical properties of biocrude were measured by the international standard/protocol (ASTM D7544 and/or EN 16900 test method) to harness biocrude as bioenergy and an initial feedstock for diverse chemicals. All measurements in this study demonstrated that the heating value, moisture content, and ash contents in biocrude were highly contingent on the type of biomass. Moreover, characterization of biocrude in this study significantly suggested that additional unit operations for char and metal removal must be conducted to meet the fuel standard in terms of biocrude as bioenergy.
Assuntos
Biocombustíveis , Pirólise , Biomassa , Temperatura Alta , Óleos de Plantas , PolifenóisRESUMO
To begin gene transcription, several transcription factors must bind to specific DNA sequences to form a complex via DNA-protein interactions. We established an in vitro method for specific and sensitive analyses of DNA-protein interactions based on a DNA immunoprecipitation (DIP) method. We verified the accuracy and efficiency of the DIP assay in quantitatively measuring DNA-protein binding using transcription factor CP2c as a model. With our DIP assay, we could detect specific interactions within a DNA-CP2c complex, with reproducible and quantitative binding values. In addition, we were able to effectively measure the changes in DNA-CP2c binding by the addition of a small molecule, FQI1 (factor quinolinone inhibitor 1), previously identified as a specific inhibitor of this binding. To identify a new regulator of DNA-CP2c binding, we analyzed several CP2c binding peptides and found that only one class of peptide severely inhibits DNA-CP2c binding. These data show that our DIP assay is very useful in quantitatively detecting the binding dynamics of DNA-protein complex. Because DNA-protein interaction is very dynamic in different cellular environments, our assay can be applied to the detection of active transcription factors, including promoter occupancy in normal and disease conditions. Moreover, it may be used to develop a targeted regulator of specific DNA-protein interaction.
Assuntos
Proteínas de Ligação a DNA/metabolismo , DNA/metabolismo , Imunoprecipitação/métodos , Fatores de Transcrição/metabolismo , Sequência de Aminoácidos , Animais , Linhagem Celular Tumoral , DNA/análise , Proteínas de Ligação a DNA/análise , Humanos , Camundongos , Ligação Proteica , Fatores de Transcrição/análiseRESUMO
We have developed an efficient method for the synthesis of 2,3-disubstituted indoles from alkyne iminoethers 1 that employs a domino process involving Ag-catalyzed condensation followed by a tandem Ag-induced cycloisomerization and 1,3-alkenyl shift to Ag-activated carbon. This methodology can be useful in regioselectively constructing 3-alkylated indoles, which are part of the structures of biologically active compounds and important alkaloids.
Assuntos
Alcenos/química , Imidoésteres/química , Prata/química , Catálise , Indóis/química , IsomerismoRESUMO
We report the short synthesis of two natural products, rosmaridiphenol and taxamairin B, from key intermediates 5a and 5b, which were prepared from enynals 8a and 9b, respectively, by using a gold-catalyzed cyclization reaction. This approach can be widely applied in the synthesis of [6,7,6]-fused tricyclic compounds found in many icetexane diterpenoids.
RESUMO
Atom-economical syntheses of isomeric 5-acetoxy-2-alkyl-2-cyclopentenones (2) and acetoxymethyl alpha-alkylallenones (3) have been described via Au-catalyzed hydrative rearrangement of 1,1-diethynylcarbinol acetates (1). In anhydrous condition, Au(I)-catalyzed [3,3]-rearrangement of 1 afforded the 3-alkynylallenyl acetate 4 in low yield. Treatment of 1 with Au(I) catalyst in wet CH(2)Cl(2) produced either 2 or 3 as a major product depending on the temperature, reaction time, and catalyst loading. D has been proposed as an intermediate, which might be formed via Au(I)-induced internal oxacyclization of the intermediate 4 followed by chemoselective nucleophilic attack by the water molecule. Formation of 2 or 3 might be explained via sequential 1,3-dioxole ring opening and gold-promoted 5-endo-dig carbocyclization or simple protonation of the intermediate D, respectively.
Assuntos
Acetatos/química , Ciclopentanos/síntese química , Ouro/química , Cetonas/química , Metanol/análogos & derivados , Metanol/química , Compostos Organoáuricos/química , Catálise , Ciclopentanos/química , Estrutura Molecular , EstereoisomerismoRESUMO
A simple, mild, catalytic and efficient method for the straightforward synthesis of an interesting class of 2-aryl/alkyl-substituted-3-indolyl quinones in good to high yields is reported for the first time. This atom-efficient method proceeds via copper-catalyzed one-pot sequential intramolecular hydroamination (C-N bond formation) of 2-alkynylanilines followed by oxidative C-C coupling with benzoquinones.
RESUMO
[structure: see text]. We have discovered a new method employing Pd-catalyzed cycloreduction of conjugated enynals 1 bearing an alkyne unit leading to the corresponding 2-(2-methylenecycloalkyl)-furans 2a-j and a related compound 7 in good to excellent yields.
RESUMO
[reaction: see text] A new and novel Au-catalyzed cycloisomerization of ynals bearing a pendant unsaturated bond leading to synthetically valuable [6.7.n]-tricyclic compounds were developed. This study strongly supports the intermediacy of [3 + 2] cycloaddition proposed by DFT calculation and provides an easy access to key skeletons found in a variety of natural products.
RESUMO
o-(1,6-Enynyl)benzaldehydes underwent a novel mode of cycloaddition using Rh(I)-precatalyst, via[3+2] cycloaddition of presumed dipolar carbonyl ylide intermediate generated by Rh-catalyst and the utility of this mechanistically intriguing enyne cyclization can be found in a number of polycyclic natural product skeletons.
RESUMO
A palladium [2 + 2] cycloaddition of 1,6- and 1,7-allenyne carboxylates and microwave-mediated [2 + 2] cycloaddition of various 1,n-allenynes were developed and, particularly, the microwave irradiated [2 + 2] cycloaddition of allenynes can provide a simple, general and eco-friendly synthetic method to fused bicyclo[m,2,0]alkadienes.
RESUMO
[reaction: see text] Unusual palladium-catalyzed arylative fragmentations of acyclic 3-allen-1-ols were observed. Oxidative addition of Pd(0) to aryl halides would form the arylpalladium halides, which added to the central carbon of allenes via carbopalladation to form the pi-allylpalladium intermediates. The pi-allylpalladium intermediates would be reductively eliminated via carbon-carbon cleavage to give the arylated dienes and the alpha-hydroxyalkylpalladium intermediates, which were further reductively eliminated to the corresponding aldehydes.
RESUMO
The Pd-catalyzed reaction of unsymmetrical alkynes with organoboronic acids gave a mixture of products and, whose ratios were controlled by the electronic as well as steric effects of the substrates.
RESUMO
The palladium-catalyzed addition reaction of alkenyl- or aryl-boronic acids into various allenes is described, which allows C-C bond formation in a highly regioselective manner under very mild conditions.
RESUMO
Isochromenylium-4-ylplatinum(II) species, generated from 1-(2-alkynylphenyl)hex-5-en-1-ones and Pt(II), reacted with a pendant olefin via [3+2] cycloaddition to form tetracyclic Pt-carbene complexes, which underwent C-H insertion with a benzyloxy group at δ or ε positions to give highly complex polycycles, which are otherwise hard to access.
RESUMO
Various 2-[6-en-1-ynyl]benzaldehydes and their analogues were successfully cyclized via Huisgen-type [3+2] cycloaddition to the tetracyclic platinum-carbene complex, which would subsequently undergo hydration to afford the tricyclic products in good yields with excellent stereoselectivities. This hydrative cyclization was also applied to the faveline synthesis.
Assuntos
Benzaldeídos/química , Dibenzocicloeptenos/síntese química , Compostos Organoplatínicos/química , Platina/química , Antineoplásicos/síntese química , Antineoplásicos/química , Benzaldeídos/síntese química , Catálise , Ciclização , Dibenzocicloeptenos/química , Estrutura Molecular , EstereoisomerismoRESUMO
2-(3-Benzyloxy)prop-1-ynyl)benzaldehyde with PtCl(2) in toluene would form Pt-pyryliums that underwent [3+2] cycloaddition with alkenes to the oxygen-bridged (5H-benzo[7]annulen-5-ylidene)platinum(ii) intermediates with good stereoselectivities. Their tandem rearrangement afforded diverse types of polycycles depending on the electronic nature of the alkenes.