Biosynthesis of anthraquinone derivatives in a Sesamum indicum hairy root culture

In order to investigate the intermediacy of 2-(4-methylpent-3-en-1-yl)anthraquinone (MPAQ), a possible intermediate for the biosynthesis of anthraquinone derivatives in sesame (Sesamum indicum), ²H-labeled MPAQ was administered to a hairy root culture of S. indicum. Efficient conversion of fed MPAQ to 2-[(Z)-4-methylpenta-1,3-dien-1-yl]anthraquinone ((Z)-MPDEAQ) was observed. Furthermore, administration experiment with ²H-labeled 2-geranyl-1,4-naphthohydroquinone, another possible intermediate, showed that it was converted to MPAQ and (Z)-MPDEAQ. The results clearly demonstrated that these substrates are the actual precursors for the production of (Z)-MPDEAQ. In contrast, neither MPAQ nor 2-geranyl-1,4-naphthohydroquinone was converted to anthrasesamone B and 2,3-epoxyanthrasesamone B, other anthraquinone derivatives in the hairy roots, suggesting that these substrates may not be the common precursors in the biosynthesis of anthraquinone derivatives.     

Isolation and Photoisomerization of a New Anthraquinone from Hairy Root Cultures of Sesamum indicum

An unstable anthraquinone was isolated from hairy root cultures of Sesamum indicum after preventing light throughout all experimental procedures. The structure of the (Z)-isomer of a previously isolated anthraquinone was determined to be 2-[(Z)-4-methylpenta-1,3-dien-1-yl]anthraquinone by spectroscopic methods. This compound was readily isomerized to the known (E)-isomer under light.     

Anthrasesamones D and E from Sesamum indicum Roots

Two anthraquinone derivatives, named anthrasesamones D and E, were isolated from the roots of Sesamum indicum. Their respective structures were determined to be 1,2,4-trihydroxy-3-(4-methylpent-3-enyl)anthraquinone and 1,2-dihydroxy-3-(4-methylpent-3-enyl)anthraquinone on the basis of spectroscopic evidence.     

Sequence-specific DNA damage induced by carcinogenic danthron and anthraquinone in the presence of Cu(II), cytochrome P450 reductase and NADPH

The mechanism of metal-mediated DNA damage by carcinogenic danthron (1,8-dihydroxyanthraquinone) and anthraquinone was investigated by the DNA sequencing technique using ³²P-labeled human DNA fragments obtained from the human c-Ha-ras-1 proto-oncogene and the p53 tumor suppressor gene. Danthron caused DNA damage particularly at guanines in the 5′-GG-3′, 5-GGGG-3′, 5′-GGGGG-3′ sequences (damaged bases are underlined) in the presence of Cu(II), cytochrome P450 reductase and the NADPH-generating system. The DNA damage was inhibited by catalase and bathocuproine, suggesting the involvement of H₂O₂ and Cu(I). The formation of 8-oxo-7,8-dihydro-2′-deoxyguanosine increased with increasing concentration of danthron. On the other hand, carcinogenic anthraquinone induced less oxidative DNA damage than danthron. Electron spin resonance study showed that the semiquinone radical could beproduced by P450 reductase plus NADPH-mediated reduction of danthron, while little signal was observed with anthraquinone. These results suggest that danthron is much more likely to be reduced by P450 reductase and generate reactive oxygen species through the redox cycle, leading to more extensive Cu(II)-mediated DNA damage than anthraquinone. In the case of anthraquinone, its hydroxylated metabolites with similar reactivity to danthron may participate in DNA damage in vivo. We conclude that oxidative DNA damage by danthron and anthraquinone seems to be relevant for the expression of their carcinogenicity.     

Anthraquinones as phytoalexins in cell and tissue cultures of Cinchona spec.

The addition of autoclaved mycelia of Aspergillus niger and the known phytopathogenic fungus Phytophtora cinnamomi to cultured cells of Cinchona ledgeriana Moens. caused a marked increase in the anthraquinone content of the plant cells. This finding in combination with the antimicrobial activity of the anthraquinones isolated from calli of Cinchona pubescens Vahl. led to the conclusion that anthraquinones are phytoalexins.Abbreviations 2,4-D 2,4-dichlorophenoyacetic acid - TLC thin-layer chromatography - AQ anthraquinone - DW dry weight     

Capoamycin,a New Isotetracenone Antibiotic

A new antibiotic was obtained from the cultured broth of an actinomycete identified as Streptomyces capoamus, and has been named capoamycin. The structure of capoamycin was elucidated by NMR spectral analysis and chemical degradation, which revealed that capoamycin was composed of a modified benz[a]anthraquinone chromophore, a β-C-olivoside and (E,E)-2,4- decadienoic acid. Capoamycin inhibited the growth of Gram-positive bacteria, yeasts and fungi, induced differentiation of mouse myeloid leukemia cells (M1) and prolonged the survival periods of mice bearing Ehrlich ascites carcinoma.     

Simultaneous determination of naphthalene and anthraquinone derivatives in Rumex nepalensis Spreng. roots by HPLC: comparison of different extraction methods and validation

Introduction – Rumex nepalensis contains mainly anthraquinone and naphthalene derivatives. Although HPLC methods have been reported for the analysis of anthraquinones, neither a phytochemical analysis of Rumex species nor the simultaneous determination of anthraquinone and naphthalene derivatives in other samples has been reported so far. Objective – To develop and validate a HPLC method for the simultaneous determination of anthraquinone and naphthalene derivatives in R. nepalensis roots. Methodology – Anthraquinones and naphthalenes were extracted from R. nepalensis roots by three methods (reflux, ultrasonication and pressurized liquid extraction) using methanol. Separation was achieved on an RP C₁₈ column with a gradient mobile phase consisting of 0.05% orthophosphoric acid in water (solvent A) and methanol (solvent B) using a UV detector (254 nm). Results – Small differences were observed in the contents of anthraquinone and naphthalene derivatives extracted by the three methods. Chrysophanol‐8‐O‐β‐D‐glucopyranoside and nepodin were detected as major constituents. The method showed a good linearity (r² > 0.9992), high precision (RSD < 5%) and a good recovery (97–105%) of the compounds. The lowest detection limit was found to be 0.97 ng and the method was found to be robust. Conclusion – Reflux and ultrasonication were found to be the best suited methods for the extraction of glycosides and aglycones, respectively. The developed and validated HPLC method is simple, precise and accurate; and can hence be recommended as the method of choice for the analysis of anthraquinones and naphthalenes in R. nepalensis and other Rumex species for both quality control as well as routine analytical purposes. Copyright © 2010 John Wiley & Sons, Ltd.     

Monomeric and Dimeric 9‐O Anthraquinone and Phenanthryl Derivatives of Cinchona Alkaloids as Chiral Solvating Agents for the NMR Enantiodiscrimination of Chiral Hemiesters

Mono‐ and bis‐alkaloid chiral auxiliaries with anthraquinone or phenanthryl cores were probed as chiral solvating agents (CSAs) for the enantiodiscrimination of chiral cyclic hemiesters. The dimeric anthraquinone derivative and the monomeric phenanthryl one showed remarkable efficiency in the nuclear magnetic resonance (NMR) differentiation of enantiomeric mixtures of hemiesters. An anthraquinone analogous with a single alkaloid unit was remarkably less effective. The conformational prevalence of the chiral auxiliaries were ascertained by NMR. Chirality 27:693–699, 2015. © 2015 Wiley Periodicals, Inc.     

Biological Activity of the Constituents in Roots of Ezo-no-gishigishi (Rumex obtusifolius)

The roots of Ezo-no-gishigishi (Rumex obtusifolius) contained a high concentration of malonic acid (more than 100 mg/100 g fr.wt) and oxalic acid (15-45 mg/100g fr.wt). The effect of several compounds isolated from the roots of R. obtusifolius on the growth of some fungi, bacteria and lettuce seedlings was examined. It is suggested that one reason for the resistance to decomposition of roots of R. obtusifolius in soil is the existence of organic acids and derivatives of naphthalene and anthraquinone in the tissue.     

Effects of nutritional factors on the formation of Anthraquinones in callus cultures of Rheum ribes

Rheum ribes L. (Polygonaceae) is the source of one of the most important crude drugs in Asiatic regions .The medicinal character of rhubarb is due to its anthraquinone content . Different parts of sterile seedlings were cultured on MS medium to study the generation of callus. The explants were cultured with different ranges of plant growth regulators and the best range of plant growth regulators for generation of callus was IBA (1 mg l^–1) and BA (1 mg l^–1). The content of anthraquinones were determined by HPLC . The concentration of sucrose, vitamins and Myo-inositol and ratio of NO₃ to NH₄ in the medium was changed and growth rate and content of 2 anthraquinones was determined . The growth rate of callus declined with increased rate of secondary metabolites production. Myo-inositol 100 mg l^–1 in the medium increased anthraquinone content and in medium that had NO₃/NH₄:1/1 the maximum content of anthraquinone was obtained.     

Decolourisation of anthraquinone-and anthracene-type dyes by versatile peroxidases from bjerkandera fumosa and pleurotus ostreatus D1

The catalytic properties of a versatile peroxidase from Pleurotus ostreatus D1 (Jacquin) P. Kummer were studied in comparison with that of a typical versatile peroxidase from Bjerkandera fumosa 137 (Per.:Fr) Karst. Decolourisation activities of both enzymes towards a wide range of dyes containing condensed aromatic rings (anthraquinone- and anthracene-type) were found. The anthraquinone dyes were decolourised rapidly by both tested peroxidases. The presence of polymerisation reaction products of Acid Blue 62, Basic Blue 22 and Reactive Blue 4 oxidation, and breakdown of aromatic rings of Alizarin Red were observed. The main catalytic constants (KM and Vmax) of the decolourisation reactions of anthraquinone dyes were calculated. In the case of Alizarin Red, inhibition of the activity of versatile peroxidase from P. ostreatus D1 by an excess of the substrate was observed. Independence from Mn²⁺ ions of the catalytic activity of versatile peroxidase from P. ostreatus D1 towards different substrates was revealed. Finally, differences in the catalytic activity towards anthracene-type dyes and monoaromatic substrates of both peroxidases were found.     

Effect of chitosan elicitation and media components on the production of anthraquinone colorants in madder (Rubia akane Nakai) cell culture

To increase the production of anthraquinone colorants in madder (Rubia akane Nakai) cell culture, the effects of elicitation on the colorant production were investigated. Chitosan was the best biotic elicitor among nine plant derived and microbial derived polysaccharides. When elicited with 25 mg/L chitosan, the total production was increased approximately two times in a seven-day culture as compared to that in the unelicited cells. Anthraquinone production was increased in proportion to the contact period up to day 3. Maximum anthraquinone colorants were obtained with 3-day treatment of chitosan. During chitosan elicitation, the total production was increased 1.3 times in MS medium containing galactose as compared to that containing sucrose. The degree of deacetylation in chitosan and the use of growth regulator or addition of precursor did not affect the production of anthraquinone colorants. When madder cells were elicited at optimum condition, anthraquinone concentration and specific anthraquinone content increased 1.3 times (0.69 g/L) and 2.2 times (0.32 g/g DCW), respectively.     

Synthesis and Antioxidant Evaluation of O-Methylated Emodacidamides: Starting from Parietin,a Secondary Metabolite of Lichen Xanthoria parietina

Polyhydroxy-anthraquinones bearing amino acids are found rather seldom in nature. Emodacidamides, isolated from a marine-derived fungus, Penicillium sp. SCSIO sof101 by Luo et al. (2017) are the first natural example of amino acid conjugated anthraquinone. In this study, O-methylated emodacidamides and emodinic acid-anilides were synthesized starting from parietin, extracted from the lichen Xanthoria parietina (L.) Th. Fr. The structural elucidations of prepared compounds were confirmed by 1D and 2D NMR analyses including HSQC and HMBC techniques. In addition, all newly synthesized compounds were evaluated for the antioxidant activities with free radical 1,1-diphenyl-2-picrylhydrazyl (DPPH) scavenging. The synthesized compounds showed low to moderate antioxidant and DPPH scavenging activities. The antioxidant activities were supported within quantum chemical calculations using the DFT−B3LYP/6-311++G(d,p) level of theory. It is observed that the antioxidant activity of emodacidamides mostly depends on the phenolic groups on anthraquinone ring. The phenolic groups on other substituents help to improve antioxidant activity and also the position of hydroxy group is a decisive factor for antioxidant ability.     

唐古特大黄(Rheum tanguticum Maxim. ex Balf.)功效组分地理变异及气候响应特征

通过研究道地药材唐古特大黄（Rheum tanguticum Maxim.ex Balf.）四种功效组分的地理变异,以及与多层次气候因子间的响应关系,揭示唐古特大黄不同化学型形成的生态学机制。运用聚类方法研究唐古特大黄成分地理变异的空间规律,并利用相关系数法分析气候因子与唐古特大黄成分的响应关系。结果表明：唐古特大黄功效组分存在明显的地理变异。青海和甘肃地区的唐古特大黄属于结合蒽醌化学生态型;而四川所产唐古特大黄为游离蒽醌化学生态型。不同时间尺度气候因子与唐古特大黄组分间的响应特征为：结合蒽醌类物质与年均温呈强负相关,多酚类物质与年均温和年降水为负相关,而与年均日照时数为正相关;结合蒽醌类物质与最冷季节温度是强负相关,多酚类物质与最冷季节温度和最湿季降雨量呈强负相关;月均温和月均日照对结合蒽醌类物质和多酚类物质影响大,其中1月至6月平均气温和9月至12月平均气温与蒽醌类物质呈强负相关,多酚类物质与5月日照量、6月日照量和7月日照量表现出强正相关。地区间的温度和日照量差异是唐古特大黄不同化学型形成的气候原因。最冷季的低温和最湿季的日照量是影响唐古特大黄品质的关键气候因子和主要时间窗口。温度浮动大,日照量高且降水量少的低温区域有助于结合蒽醌类和多酚类物质的形成和累积。     

Growth,differentiation and secondary metabolites of colour mutants ofTrichoderma viride

The parental strainTrichoderma viride and 3 colour mutants (milk white, yellow and brown) blocked at various stages of colony pigmentation derived from it were characterized. The parental strain and the mutants exhibited different growth rates. The identical type of induced fluorescence was observed in all the strains. Hyphae and septa lighted first, whereas reproduction structures did not; after treatment with fluorescein-isothiocyanate and Blankophor RKH the growing hyphal apices were accentuated. In the mutants conidiation was induced at 1-, 2- and 3-d intervals, similarly to the parent strain. Pigmentation of conidiation rings depended on their type and age. The yellow and brown mutants excreted chromatographically different pigments, extractable with ethylacetate, into the medium. Two anthraquinone pigments,viz. 1,3,6,8-tetrahydroxyanthraquinone (1) and 1-acetyl-2,4,5,7-tetrahydroxyanthraquinone (2) were isolated from the brown mutant (Betinaet al. 1986).     

Controlled transformation from nanorods to vesicles induced by cyclomaltoheptaoses (β-cyclodextrins)

A modified cyclomaltoheptaose (β-cyclodextrin) containing an anthraquinone moiety, mono[6-deoxy-N-n-hexylamino-(N′-1-anthraquinone)]-β-cyclodextrin (1), which can self-assemble into nanorods in aqueous solution, was synthesized. Interestingly, upon the addition of natural cyclodextrin, the nanorods could transform into bilayer vesicles, which were characterized by transmission electron microscopy (TEM), scanning electron microscopy (SEM), dynamic light scattering (DLS), and epi-fluorescence microscopy (EFM). A transformation mechanism is suggested based on the results of ¹H NMR, 2D NMR ROESY, FTIR, and UV–vis spectra. The response of the vesicles to changing pH and adding Cu²⁺ was also tested. Our research may pave the way to the development of new intelligent materials and biomaterials.     

Studies on the Metabolic Products of Macrosporium Porri Elliott

Macrosporin monoluethylether was synthesized by means of condensation between α-resorcylic acid (I) and 3-methoxy-p-toluic acid (II) with the use of conc. sulfuric acid and boric anhydride.

From this result macrosporin C₁₆H₁₂O₅, a metabolic product of Macrosporium Porri Elliott, was established to be 3,5-dihydroxy-7-methoxy-2-methyl anthraquinone (A).     

Agrobacterium rhizogenes-mediated transformation of Rubia peregrina L.: in vitro accumulation of anthraquinones

An Agrobacterium rhizogenes-mediated transformation system for Rubia peregrina L. has been established by co-cultivation of callus cultures or by direct infection of explants with A. rhizogenes LBA 9402 harbouring the binary vector pMON 9703 containing gus and npt-II genes as markers. The putative transformed roots were selected on medium containing kanamycin (25 mg l^-1). Antibiotic resistant root clones were subjected to histochemical analysis for the localisation of -glucuronidase activity. Polymerase chain reaction was used to confirm the presence of gus, npt-II and T _L border sequences in the transformed root clones. Spontaneous regeneration of shoots was observed from 30 day-old transgenic roots. Total anthraquinone and alizarin contents of transgenic root cultures were measured by spectrophotometry and by high performance liquid chromatography. The accumulation of total anthraquinones in transformed roots was found to be approximately 2-fold higher than that found in one year-old field grown roots (2.12±0.12 and 1.23±0.12 mg g^-1 dry weight, respectively). Alizarin was found to be the major anthraquinone in transformed root cultures and was found to be approximately 3-fold higher than in field grown roots.Abbreviations BA 6-benzyladenine - B5 Gamborg B5 medium - gus -glucuronidase gene - GUS -glucuronidase - HPLC high performance liquid chromatography - MS Murashige and Skoog medium - NAA -naphthalene acetic acid - npt-II neomycin phosphotransferase II gene - OD₆₀₀ optical density at 600 nm - PCR polymerase chain reaction - T _L left border sequence of T-DNA - vir D1 virulence D1 gene - YMB yeast mannitol broth     

Enzymes from spent mushroom substrate of <Emphasis Type="Italic">Pleurotus sajor</Emphasis>-<Emphasis Type="Italic">caju</Emphasis> for the decolourisation and detoxification of textile dyes

The potential of ligninolytic enzymes, including lignin peroxidase (LiP) as the main enzyme from the spent mushroom substrate of Pleurotus sajor-caju was evaluated for the decolourisation of five dyes from azo and anthraquinone dye groups. Among the azo dyes, reactive black 5 and reactive orange 16 were 84.0 and 80.9% decolourised respectively, after 4 h of incubation with 45 U of LiP as compared to 32.1% decolourisation of disperse blue 79. Among the anthraquinone dyes, disperse red 60 was decolourised to 47.2% after 4 h of incubation with 45 U of LiP as compared to 5.9% decolourisation of disperse blue 56. Increasing the LiP concentration and incubation time had a positive effect on the decolourisation of anthraquinone dyes as compared to azo dyes. A 67.9% decolourisation of synthetic textile waste-water was achieved after 4 h of incubation with 25 U of LiP. Increasing the incubation time significantly increased (P < 0.05) the decolourisation of synthetic textile waste-water. Further, there was a 52.4% reduction in the toxicity of synthetic textile waste-water treated with 55 U of LiP for 4 h. However, only 35.7% reduction in toxicity was achieved when the synthetic textile waste-water was treated with 55 U of LiP for 24 h. In this study, it was shown that the spent mushroom substrate of P. sajor-caju could be a cheap source of ligninolytic enzymes for the decolourisation of dyes in textile industry wastewaters.     

Identification of Anthraquinone-Degrading Bacteria in Soil Contaminated with Polycyclic Aromatic Hydrocarbons

Quinones and other oxygenated polycyclic aromatic hydrocarbons (oxy-PAHs) are toxic and/or genotoxic compounds observed to be cocontaminants at PAH-contaminated sites, but their formation and fate in contaminated environmental systems have not been well studied. Anthracene-9,10-dione (anthraquinone) has been found in most PAH-contaminated soils and sediments that have been analyzed for oxy-PAHs. However, little is known about the biodegradation of oxy-PAHs, and no bacterial isolates have been described that are capable of growing on or degrading anthraquinone. PAH-degrading Mycobacterium spp. are the only organisms that have been investigated to date for metabolism of a PAH quinone, 4,5-pyrenequinone. We utilized DNA-based stable-isotope probing (SIP) with [U-¹³C]anthraquinone to identify bacteria associated with anthraquinone degradation in PAH-contaminated soil from a former manufactured-gas plant site both before and after treatment in a laboratory-scale bioreactor. SIP with [U-¹³C]anthracene was also performed to assess whether bacteria capable of growing on anthracene are the same as those identified to grow on anthraquinone. Organisms closely related to Sphingomonas were the most predominant among the organisms associated with anthraquinone degradation in bioreactor-treated soil, while organisms in the genus Phenylobacterium comprised the majority of anthraquinone degraders in the untreated soil. Bacteria associated with anthracene degradation differed from those responsible for anthraquinone degradation. These results suggest that Sphingomonas and Phenylobacterium species are associated with anthraquinone degradation and that anthracene-degrading organisms may not possess mechanisms to grow on anthraquinone.