7598-10-9

Synthesis of retinoic acid analogs involving an anthraquinone ring is described. The reaction of p-toluenesulfonylmethylanthraquinones 8 with ethyl 8-chloro-3,7-dimethyl-2,4,6-octatrienoate (6) and subsequent desulfonylation afforded the esters 10 and 11 as a mixture of terminal double bond isomers. After separation of these isomers, basic hydrolysis using 10% potassium hydroxide gave the corresponding acids 12 and 13, respectively, without isomerization of the terminal double bond in excellent yields.

Herein, a new type of fluorescent probe core, (E)-2-styrylanthracene-9,10-dione (EK01), was developed which displayed strong fluorescence quantum yield (Φ = 0.867 in DMF; Φ = 0.561 in acetone; Φ = 0.616 in CH2Cl2; Φ = 0.265 in DMSO), good photostability, large stokes shift (90 nm–120 nm) and molar extinction coefficients (0.5875 × 104–0.7609 × 104 mol?1 L cm?1). During cell assays and co-localization experiments, EK01 showed excellent cell membrane permeability and low cytotoxicity against MCF-10A (human mammary epithelial cell line) and HT-29 (human colorectal adenocarcinoma cell line). Particularly, we surprisingly discovered that EK01 could selectively aggregate in mitochondria and specific stain it in a green emissive fluorescent form, which means that EK01 could be a real-time specifically monitor of mitochondria in living cells with a high signal-to-noise ratio. Hence a new mitochondria imaging method was established which is incubating EK01 with living cells for 1 h at a final concentration of 6–12 μM, then visualizing under a confocal microscope at 395 nm. It is worth noting that the fluorescence efficiency of EK01 is not outstanding in organisms, it has much stronger fluorescence efficiency in other organic solvent systems (such as DMF, acetone and CH2Cl2). Therefore, as a new type of fluorescent core that is easy to synthesis and graft, we believe that (E)-2-styrylanthracene-9,10-diones have the potential to develop a variety of fluorescence platforms applying in different fields.

The invention provides a novel D-A type tetracyano-anthraquinone dimethane small molecule acceptor material as well as a preparation method and application thereof. The structure of the acceptor material is shown as a formula I in the specification. The small molecule acceptor material has good solubility and stability, has good matching of absorption spectrum and solar spectrum, and can be used in the field of solar cell materials.

The invention relates to a tetracyano-anthraquinone dimethane micromolecular acceptor material as well as a preparation method and application thereof. The structure of the acceptor material is as shown in a formula I, which is described in the specification. The micromolecular acceptor material has good solubility and stability, the absorption spectrum is well matched with the solar spectrum, andthe micromolecular acceptor material can be used for organic solar cells.

The present disclosure provides an antibacterial hydrophilic compound. The antibacterial hydrophilic compound may react, induced by light through a hydrogen abstraction group in the structural formula thereof, with a C—H group and thus bind to a surface of a material having the C—H group (for example, chemical fibers such as polyester, chinlon, and the like; plastics, rubbers, and other similar materials), which can impart a durable antibacterial activity and hydrophilicity to the material. The antibacterial hydrophilic compound has a relatively strong binding force to the surface of the material without damaging the mechanical properties of the raw material. The present disclosure also provides a modified material that is modified by the antibacterial hydrophilic compound.

Anthraquinone (AQ) compounds have been used as photolabile protecting groups (PPGs) to protect alcohols, ketones, and carboxylic acids. However, because of the lack of direct spectroscopic information for the transient species and intermediates related with the deprotection reaction(s), the photorelease mechanism(s) of these systems are still largely unknown. In this contribution, we detail a time-resolved spectroscopic investigation using anthraquinone-protected galactose (1) and adenosine (2) to investigate the photodeprotection reaction mechanism(s) of these kinds of AQ-PPGs. It was found that, in THF-H2O solvents, the ketyl radical species generated for 1 and 2 was found to be a reactive intermediate that then formed a dihydroxyanthracene species. The photodeprotection then occurred with the accompaniment of a decarboxylation process. These results provide an improved understanding for how AQ-PPGs work and will help assist in the design and applications of selected anthraquinone derivatives as a PPG platform, especially in aqueous environments more relevant for use in biological systems.

Emodin, a natural anthraquinone derivative isolated from Rheum palmatum L., has been demonstrated to exhibit good anti-cancer effect. In this study, a series of novel quaternary ammonium salts of emodin, anthraquinone and anthrone were synthesized and their anticancer activities were tested in vitro. The effects of emodin quaternary ammonium salts on cell viability, apoptosis, intracellular ROS, and mitochondrial membrane potential were investigated in A375, BGC-823, HepG2 and HELF cells. The results demonstrated that compound 4a induced morphological changes and decreased cell viability. Apoptosis triggered by compound 4a was visualized using DAPI staining and Annexin V-FITC/PI staining. Compound 4a-induced apoptosis of A375 cells were showed to be associated with the dissipation of mitochondrial membrane potential (ΔΨm) as a result of the up-regulation of P53 and Caspase-3. When cancer cells were treated with emodin derivative, their ability to generate reactive oxygen species (ROS) rose significantly and the mitochondrial membrane potential decreased. Additionally, confocal microscopy assay confirmed that compound 4a was primarily located in the mitochondria of A375 cells. These results suggested that compound 4a has the potential for use in cancer therapy.

The invention discloses preparation methods for anthraquinone and naphthoquinone quaternary ammonium salts with leukemia resisting function. The preparation method for the anthraquinone quaternary ammonium salts comprises the steps: enabling emodin N-bromo succimide to be subjected to bromination reaction in the presence of benzoyl peroxide, so as to produce 2-bromo methylanthraquinone; and enabling 2-bromo methylanthraquinone to be subjected to nucleophilic substitution reaction with methyldioctyl tertiary amine or methyl didecyl tertiary amine, thereby producing the anthraquinone quaternary ammonium salts. The preparation method for the naphthoquinone quaternary ammonium salts comprises the steps: enabling 2-hydroxyl naphthoquinone and 1,4-dibromobutane to be subjected to Williamson etherification reaction in the presence of K2CO3, so as to produce bromobutoxyl naphthaquinone; and enabling bromobutoxyl naphthaquinone to be subjected to nucleophilic substitution reaction with methyldioctyl tertiary amine, thereby producing the corresponding naphthoquinone quaternary ammonium salts. Proven by experiments, the anthraquinone and naphthoquinone quaternary ammonium salts prepared by the preparation methods have relatively strong inhibiting actions on leukemia cells, and the anti-cancer activity of the anthraquinone and naphthoquinone quaternary ammonium salts is higher than that of a precursor 2-methylanthraquinone by over 50 times, so that the anthraquinone and naphthoquinone quaternary ammonium salts have an application prospect of becoming leukemia resisting drugs.

A series of (1H-1,2,3-triazol-4-yl)methoxybenzaldehyde derivatives containing an anthraquinone moiety were synthesized and identified as novel xanthine oxidase inhibitors. Among them, the most promising compounds 1h and 1k were obtained with IC50values of 0.6?μM and 0.8?μM, respectively, which were more than 10-fold potent compared with allopurinol. The Lineweaver-Burk plot revealed that compound 1h acted as a mixed-type xanthine oxidase inhibitor. SAR analysis showed that the benzaldehyde moiety played a more important role than the anthraquinone moiety for inhibition potency. The basis of significant inhibition of xanthine oxidase by 1h was rationalized by molecular modeling studies.

The invention belongs to the technical field of medicine, and particularly relates to 2-substituted-9,10-anthraquinone compounds represented by the general formula I, the general formula II, the general formula III and the general formula IV, and pharmaceutically acceptable salts, hydrates or solvates and pharmaceutically acceptable carriers thereof. A preparation method comprises the steps: with phthalic anhydride as a starting material, carrying out a Friedel-Crafts reaction, concentrated sulfuric acid dehydration, NBS bromization and sodium azide substitution, generating a key intermediate 2-azide methyl-9,10-anthraquinone, and finally in the presence of copper sulfate pentahydrate and vitamin C, carrying out a Husigen cycloaddition reaction with substituted alkyne; or carrying out concentrated sulfuric acid dehydration, cyclization, chromium trioxide oxidation and thionyl chloride chlorination, to obtain anthraquinone-2-formyl chloride, then carrying out an acylation reaction with various L-amino acid methyl esters, further hydrolyzing, and thus obtaining the target compounds. The prepared compounds show good results in in-vitro antitumor activity tests.

The photo-Ritter reaction of five arylmethyl bromides can occur in acetonitrile to give acetamides. The intermediates, carbocations, which are formed from subsequent electron transfer between the radical pairs generated from initial homolytic cleavage of the C-Br bond, are trapped by acetonitrile, and subsequent hydrolysis generates the corresponding acetamides. Taylor & Francis Group, LLC.

Photolysis (254-350 nm) of a variety of aroyl-substituted phenylacetic acids and p-acetylphenylacetic acid in aqueous solution at pH > pK(a) resulted in efficient photodecarboxylation (Φ = 0.2-0.7), to give in most cases a single product arising via the corresponding arylmethyl carbanion, indicating that photodecarboxylation is an efficient and general reaction for these types of compounds.

The synthesis of a series of donor-acceptor podands is described. The dependence of the rate constants of intramolecular photoinduced electron transfer on the exothermicity of the reaction was studied by stationary and time-resolved fluorescence spectroscopy. 1H NMR and computational studies suggest that the conformational change of the podands is restricted by K+ binding. As a result, the occurrence of highly exothermic photoinduced electron transfer reaction within the Marcus inverted region was observed.

Three new cationic amphiphiles bearing anthraquinone moieties at the polar headgroup region were synthesized. The single-chain amphiphile, N,N-dimethyl-N-octadecyl-N-(9,10-dihydro-9,10-dioxoanthracen-2-ylmethyl) ammonium bromide 1, in the presence of cetyltrimethylammonium bromide upon dispersion in water gave co-micellar aggregates containing covalently attached anthraquinone residues at the polar aqueous interfaces. The other two double-chain amphiphiles, N,N-dioctadecyl-N-methyl-N-(9,10-dihydro-9,10- dioxoanthracen-2-ylmethyl)ammoniurn bromide 2 and N,N-dimethyl-N-(1,2- bispalmitoyloxypropanyl)-N-(9,10-dihydro-9110-dioxanthracen-2-ylmethyl)ammonium bromide 3, however, on dispersion in aqueous media produced vesicular aggregates. The critical temperatures for the gel to liquid-crystalline-like phase transition processes for the vesicular systems were determined by following temperature-dependent changes in the ratios of keto-enol tautomeric forms of benzoylacetanilide doped within respective vesicular assemblies. The redox chemistry of the these supramolecular assemblies was also studied by following the time-dependent changes in the UV-VIS absorption spectroscopy in the presence of exogenous reducing or oxidizing agents. Electrochemical studies using glassy carbon electrodes reveal that redox-active amphiphiles adsorb on to the glassy carbon surfaces to form electroactive deposits when dipped into aqueous suspensions of either of these aggregates irrespective of the micellar or vesicular nature of the dispersions.

The C-alkylation reaction of three reductive alkylating agents prepared from 2-methylanthraquinone by 2-nitropropane anion is shown to proceed by the S(RN)1 mechanism. The S(RN)1 mechanism is confirmed by the leaving group effect and the inhibitory effect of dioxygen, p-dinitrobenzene, cupric chloride and di-tert-butylnitroxide. This reaction can be extended to 1-methyl-3-nitropyrolidin-2-one anion.

Salts derived from 2-nitropropane react with 2-(halomethyl)-9,10-anthracenedione or triethylammonium derivative by a SRN1 mechanism.The operation of this mechanism is confirmed by the leaving group effect and by the inhibitory effect of di-tert-butylnitroxide.A base-promoted nitrous acid elimination gives a 9,10-anthracenedione bearing a trisubstituted ethylenic double bound in the 2 position.

In order to study the electrochemical behavior of a redox species in the Langmuir-Blodgett (LB) film on a glassy carbon (GC) electrode, three kinds of amphiphilic redox compounds, each carrying an anthraquinone, a viologen and a ferrocene moiety, were confirmed on the electrode surfaces.Prior to the deposition of the film on the electrode, surface pressure-area isotherms for a number of mixed films of the redox-active amphiphiles and arachidic acid were recorded and the stability of the monolayers was discussed.Finally, the cyclic voltammetric behavior of the LB film-modified electrodes was discussed in terms of the changes in the structure and the nature of the LB film caused by the redox reactions.

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The 2-methylene-9,10-anthraquinone (Maq) ester of γ-(benzyloxycarbonylamino)butyric acid (3a) and the Maq ester of N-(3-benzyloxycarbonylpropyl)carbamic acid (4) were synthesized as possible γ-aminobutyric acid (GABA) delivery systems.Electrochemical reduction of these Maq esters at -0.5 V (SCE) in 50percent aqueous THF buffer (pH 7.0) produced their corresponding anthrahydroquinones, which failed to give detectable cleavage products after several hours.In contrast, reduction of 3a and 4 in DMF at -0.9 V (-1.2 V) produced their radical anions (dianions), which formed theMaq cleavage products 2-methyl-9,10-anthraquinone and 2-(hydroxymethyl)-9,10-anthraquinone in combined yields of >80percent.Comparable yields of the other cleavage products, the GABA esters, were also found.This work demonstrates that electrochemical reduction can be used as an alternative method for deprotection of Maq esters of carboxylic acids used in the synthesis of peptides.In addition, the synthesis of 4 and its reductive cleavage shows that Maq esters of carbamates can serve as protecting groups of primary amines.

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