Inhibition of lipopolysaccharide-induced NF-κB maintains osteogenesis of dental pulp and periodontal ligament stem cells.

Dental pulp stem cells (DPSCs) and periodontal ligament stem cells (PDLSCs) can differentiate into osteoblasts, indicating that both are potential candidates for bone tissue engineering. Osteogenesis is influenced by many environmental factors, one of which is lipopolysaccharide (LPS). LPS-induced NF-κB activity affects the osteogenic potencies of different types of MSCs differently. This study evaluated the effect of LPS-induced NF-κB activity and its inhibition in DPSCs and PDLSCs. DPSCs and PDLSCs were cultured in an osteogenic medium, pretreated with/without NF-κB inhibitor Bay 11-7082, and treated with/without LPS. Alizarin red staining was performed to assess bone nodule formation, which was observed under an inverted light microscope. NF-κB and alkaline phosphatase (ALP) activities were measured to examine the effect of Bay 11-7082 pretreatment and LPS supplementation on osteogenic differentiation of DPSCs and PDLSCs. LPS significantly induced NF-κB activity (p = 0.000) and reduced ALP activity (p = 0.000), which inhibited bone nodule formation in DPSCs and PDLSCs. Bay 11-7082 inhibited LPS-induced NF-κB activity, and partially maintained ALP activity and osteogenic potency of LPS-supplemented DPSCs and PDLSCs. Thus, inhibition of LPS-induced NF-κB activity can maintain the osteogenic potency of DPSCs and PDLSCs.

The natural anthraquinone dye emodin: Eco/genotoxicological characterization for aquatic organisms.

Emodin is an anthraquinone secondary metabolite produced by several species of plants and fungi. Emodin is known for its pharmacological versatility, and, in the textile industry, for its good dyeing properties. However, its use in the textile industry can result in the formation and disposal of large volumes of wastewater. Emodin mutagenicity has been shown in bacteria and in human cells, but little is known about its possible toxic, genotoxic, or mutagenic effects in aquatic organisms. We have evaluated the eco/genotoxicity of emodin to aquatic organisms. Emodin was toxic to Daphnia similis (EC50 = 130 µg L-1) and zebrafish embryos (LC50 = 25 µg L-1). No toxicity was observed for Raphidocelis subcapitata, Ceriodaphnia dubia, or Parhyale hawaiensis. Additional biochemistry/molecular studies are needed to elucidate the toxic/mutagenic pathways of emodin in aquatic organisms. The PNEC value for emodin was 0.025 µg L-1. In addition to mutagenicity in the Salmonella/microsome assay, emodin was mutagenic in the micronucleus assay in the amphipod P. hawaiensis. Among the anthraquinone dyes tested to date, natural or synthetic, emodin was the most toxic to aquatic species.

Antitumoral photoinduced effects of crude extract, fractions, and naphthoquinones from Sinningia magnifica (Otto & A. Dietr.) Wiehler (Gesneriaceae) in a bioguided study.

Photodynamic therapy (PDT) has been used for various purposes, including as an antitumor resource in a noninvasive therapy with minimal side effects. Sinningia magnifica (Otto & A. Dietr.) Wiehler is a rupicolous plant found in rock crevices in Brazilian tropical forests. Initial studies indicate the presence of phenolic glycosides and anthraquinones in species of the genus Sinningia (Generiaceae family). It is known that anthraquinones are natural photosensitizers with potential PDT applications. This led us to investigate the potential compounds of S. magnifica for use as a natural photosensitizer against the melanoma (SK-MEL-103) and the prostate cancer (PC-3) cell lines in a bioguided study. Our results showed that singlet oxygen production by the 1,3-DPBF photodegradation assay greatly increased in the presence of crude extract and fractions. The biological activity evaluation showed photodynamic action against melanoma cell line SK-MEL-103 and prostate cell line PC-3. These results suggest the presence of potential photosensitizing substances, as demonstrated in this in vitro antitumor PDT study by the naphthoquinones Dunniol and 7-hydroxy-6-methoxy-α-dunnione for the first time. Naphthoquinones, anthraquinones and phenolic compounds were identified in the crude extract by UHPLC-MS/MS analysis, motivating us to continue with the bioguided phytochemical study aiming to discover more photochemically bioactive substances in Gesneriaceae plants.

Quinones: Biosynthesis, Characterization of 13 C Spectroscopical Data and Pharmacological Activities.

Quinones are natural products widely distributed in nature, which are involved in stages of several vital biological processes, with mostly having a variety of pharmacological properties. The main groups comprising most of these compounds are benzoquinones, naphthoquinones, anthraquinones, and phenanthraquinones. Quinone isolation has been a focus of study around the world in recent years; for this reason, this study approaches the junction of natural quinones identified by 13 C Nuclear Magnetic Resonance (NMR) spectroscopic analytical techniques. The methodology used to obtain the data collected articles from various databases on quinones from 2000 to 2022. As a result, 137 compounds were selected, among which 70 were characterized for the first time in the period investigated; moreover, the study also discusses the biosynthetic pathways of quinones and the pharmacological activities of the compounds found, giving an overview of the various applications of these compounds.

Corn Cob as a Green Support for Laccase Immobilization-Application on Decolorization of Remazol Brilliant Blue R.

The high demand for food and energy imposed by the increased life expectancy of the population has driven agricultural activity, which is reflected in the larger quantities of agro-industrial waste generated, and requires new forms of use. Brazil has the greatest biodiversity in the world, where corn is one of the main agricultural genres, and where over 40% of the waste generated is from cobs without an efficient destination. With the aim of the valorization of these residues, we proposed to study the immobilization of laccase from Aspergillus spp. (LAsp) in residual corn cob and its application in the degradation of Remazol Brilliant Blue R (RBBR) dye. The highest yields in immobilized protein (75%) and residual activity (40%) were obtained at pH 7.0 and an enzyme concentration of 0.1 g.mL-1, whose expressed enzyme activity was 1854 U.kg-1. At a temperature of 60 °C, more than 90% of the initial activity present in the immobilized biocatalyst was maintained. The immobilized enzyme showed higher efficiency in the degradation (64%) of RBBR dye in 48 h, with improvement in the process in 72 h (75%). The new biocatalyst showed operational efficiency during three cycles, and a higher degradation rate than the free enzyme, making it a competitive biocatalyst and amenable to industrial applications.

Determination of anthraquinones in Rhamnus purshiana using high-performance liquid chromatography coupled to diode array detector and simple ultraviolet spectroscopic analysis.

A new method based on Ultraviolet spectrophotometry was developed and compared with that based on high-performance liquid chromatography for the determination and quantification of anthraquinones in the extracts of Rhamnus purshiana bark. A validated quantitative analysis of cascaroside A, cascaroside B, emodin, and aloe-emodin in these herbal products has been previously performed using high-performance liquid chromatography coupled with a diode array detector. In the high-performance liquid chromatography analysis, all the anthraquinones showed satisfactory regression (r2 > 0.98) within the test ranges, and the recovery was in the range of 94-117%. The limits of detection and quantification were 0.008-0.010 and 0.029-0.035 µg/mL, respectively. Hierarchical cluster analysis and principal component analysis showed differences in the anthraquinones determined from herbal samples. Subsequently, a simple and low-cost ultraviolet spectrophotometric methodology for the quantitative analysis of the same compounds in the extracts was applied, and all the contents were determined. A paired t-test confirmed that there were no significant differences between the two methods. Our results revealed that the developed method is simple and provides the ability to discriminate and control the quality of anthraquinones in herbal products.

Photosensitization of a subcutaneous tumour by the natural anthraquinone parietin and blue light.

Photodynamic therapy (PDT) is an anticancer treatment involving administration of a tumour-localizing photosensitizer, followed by activation by light of a suitable wavelength. In previous work, we showed that the natural anthraquinone (AQ) Parietin (PTN), was a promising photosensitizer for photodynamic therapy of leukemic cells in vitro. The present work aimed to analyze the photosensitizing ability of PTN in the mammary carcinoma LM2 cells in vitro and in vivo in a model of subcutaneously implanted tumours. Photodynamic therapy mediated by parietin (PTN-PDT) (PTN 30 µM, 1 h and 1.78 J/cm2 of blue light) impaired cell growth and migration of LM2 cells in vitro. PTN per se induced a significant decrease in cell migration, and it was even more marked after illumination (migration index was 0.65 for PTN and 0.30 for PTN-PDT, *p < 0.0001, ANOVA test followed by Tukey's multiple comparisons test), suggesting that both PTN and PTN-PDT would be potential inhibitors of metastasis. Fluorescence microscopy observation indicated cytoplasmic localization of the AQ and no fluorescence at all was recorded in the nuclei. When PTN (1.96 mg) dissolved in dimethyl sulfoxide was topically applied on the skin of mice subcutaneously implanted with LM2 cells, PTN orange fluorescence was strongly noticed in the stratum corneum and also in the inner layers of the tumour up to approximately 5 mm. After illumination with 12.74 J/cm2 of blue light, one PDT dose at day 1, induced a significant tumour growth delay at day 3, which was not maintained in time. Therefore, we administered a second PTN-PDT boost on day 3. Under these conditions, the delay of tumour growth was 28% both on days 3 and 4 of the experiment (*p < 0.05 control vs. PTN-PDT, two-way ANOVA, followed by Sidak's multiple comparisons test). Histology of tumours revealed massive tumour necrosis up to 4 mm of depth. Intriguingly, a superficial area of viable tumour in the 1 mm superficial area, and a quite conserved intact skin was evidenced. We hypothesize that this may be due to PTN aggregation in contact with the skin and tumour milieu of the most superficial tumour layers, thus avoiding its photochemical properties. On the other hand, normal skin treated with PTN-PDT exhibited slight histological changes. These preliminary findings encourage further studies of natural AQs administered in different vehicles, for topical treatment of cutaneous malignancies.

Cellular and biochemical antileukemic mechanisms of the meroterpenoid Oncocalyxone A.

Oncocalyxone A, a 1,4-benzoquinone derived from Cordia oncocalyx, exhibits anti-inflammatory, antimicrobial and antidiabetic properties. The aim of this study was to (1) examine the cytotoxic actions of oncocalyxone A on human normal and tumor cell lines and (2) determine mechanistic actions underlying effects upon leukemia cells using cellular and molecular techniques. Antiproliferative studies on cancer cell lines, peripheral blood mononuclear cells, and human erythrocytes were performed using colorimetric assays. To understand cytotoxicity, assessments were performed with HL-60 leukemia cells (8, 16.5, or 33 µM) after 24 hr incubation using light and fluorescence microscopy, trypan blue, flow cytometry, Comet assay, western blot of caspases and poly-ADP-ribose polymerase (PARP), and effects on topoisomerase I and II. Oncocalyxone A exhibited cytotoxic action upon HL-60 cells and dividing leukocytes, but minimal hemolytic action on erythrocytes. Mechanistic investigations demonstrated reduction of cell viability, loss of membrane integrity, cell shrinking, chromatin condensation, blebbings, externalization of phosphatidylserine, caspase activation, PARP cleavage, mitochondrial depolarization, and DNA damage. Pre-treatment with N-acetylcysteine 4 mM significantly reduced DNA damage and prevented membrane integrity loss. Oncocalyxone A displayed free radical dependent antileukemic activity via apoptotic pathways and induced DNA damage in HL-60 cells. Oncocalyxone A possesses structural chemical simplicity enabling it to be a cost-effective alternative. These properties justify further improvements to enhance activity and selectivity and the development of pharmaceutical formulations. Abbreviations Acridine orange, AO; ANOVA, analysis of variance; BSA, bovine serum albumin; DI, Damage Index; DMSO, dimethylsulfoxide; EC50, effective concentration 50%; EDTA, ethylenediamine tetraacetic acid; EB, ethidium bromide; HCT-116, colon carcinoma line; HL-60, promyelocytic leukemia line; IC50, inhibitory concentration 50%; MTT, 3-(4,5-dimethyl-2-thiazolyl)-2,5-diphenyl-2H-tetrazolium bromide; OVCAR-8, ovarian carcinoma line; NAC, N-acetylcysteine, PBMC, peripheral blood mononuclear cells; PBS, phosphate-buffered saline; PI, propidium iodide; PARP, poly-ADP-ribose polymerase; RPMI-1640, Roswell Park Memorial Institute medium; SF-295, glioblastoma line; ROS, reactive oxygen species; 7-AAD, 7-amino-actinomycin D; H2-DCF-DA, 7'-dichlorodihydrofluorescein diacetate.

Phialomyces macrosporus: Chemical Constituents, Antimicrobial Activity and Complete NMR Assignments for the 7,7'-Biphyscion.

Five known secondary metabolites, chrysophanol (1), 7,7'-biphyscion (2), secalonic acid D (3), mannitol (4) and trehalose (5) were isolated for the first time from the extracts of the fungus Phialomyces macrosporus. Their structures were elucidated by NMR methods (1D and 2D NMR analysis), optical activity and ESI-MS. Complete 1 H and 13 C assignments were performed for compound 2. The antimicrobial activity was evaluated by serial microdilution assay for compounds 2 and 3 and results showed that compound 3 exhibited a significant growth inhibition at concentrations of 15.6 mg/ml (S. aureus and S. choleraesius) and 0.97 mg/mL (B. subtilis), comparable to the positive control.

The addition of a quaternary group in biopolymeric material increases the adsorptive capacity of Acid Blue 25 textile dye.

The quaternization of chitosan molecules creates materials with high adsorptive capacity towards textile dyes, which renders them capable of rapidly removing such dyes from a solution. In this study, a novel material was synthesized in bead form to adsorb the Acid Blue 25 textile dye. The adsorption isotherms, kinetics, and thermodynamics of this new material were investigated. The beads were further characterized by FT-IR and SEM studies, as well as their rheological behavior. Bioassays with Daphnia similis analyzed the toxicity of the dye before and after treatments. The Freundlich isotherm model fitted to all the adsorption data in a pH range from 2.50 to 8.50. Kinetic studies showed that adsorption was ruled by an intraparticle diffusion process and reached equilibrium in 270 min, as 39.527 µg mg-1 of dye was sorbed to the beads. Thermodynamic studies showed that adsorption was a spontaneous and endothermic process. Thermodynamics also confirmed that the adsorption was proportionally influenced by higher temperatures. The FT-IR spectroscopy identified the adsorbate/adsorbent binding sites, thus confirming the occurrence of chemisorption. Post-treatment bioassays found a significant decrease in toxicity, obtaining just 10% of D. similis mortality after adsorption treatments. Therefore, the synthesized beads from this research can potentially be applied to the treatment of textile effluents.

A screening platform to monitor RNA processing and protein-RNA interactions in ribonuclease P uncovers a small molecule inhibitor.

Ribonucleoprotein (RNP) complexes and RNA-processing enzymes are attractive targets for antibiotic development owing to their central roles in microbial physiology. For many of these complexes, comprehensive strategies to identify inhibitors are either lacking or suffer from substantial technical limitations. Here, we describe an activity-binding-structure platform for bacterial ribonuclease P (RNase P), an essential RNP ribozyme involved in 5' tRNA processing. A novel, real-time fluorescence-based assay was used to monitor RNase P activity and rapidly identify inhibitors using a mini-helix and a pre-tRNA-like bipartite substrate. Using the mini-helix substrate, we screened a library comprising 2560 compounds. Initial hits were then validated using pre-tRNA and the pre-tRNA-like substrate, which ultimately verified four compounds as inhibitors. Biolayer interferometry-based binding assays and molecular dynamics simulations were then used to characterize the interactions between each validated inhibitor and the P protein, P RNA and pre-tRNA. X-ray crystallographic studies subsequently elucidated the structure of the P protein bound to the most promising hit, purpurin, and revealed how this inhibitor adversely affects tRNA 5' leader binding. This integrated platform affords improved structure-function studies of RNA processing enzymes and facilitates the discovery of novel regulators or inhibitors.

Anti-Herpetic, Anti-Dengue and Antineoplastic Activities of Simple and Heterocycle-Fused Derivatives of Terpenyl-1,4-Naphthoquinone and 1,4-Anthraquinone.

Quinones are secondary metabolites of higher plants associated with many biological activities, including antiviral effects and cytotoxicity. In this study, the anti-herpetic and anti-dengue evaluation of 27 terpenyl-1,4-naphthoquinone (NQ), 1,4-anthraquinone (AQ) and heterocycle-fused quinone (HetQ) derivatives was done in vitro against Human Herpesvirus (HHV) type 1 and 2, and Dengue virus serotype 2 (DENV-2). The cytotoxicity on HeLa and Jurkat tumor cell lines was also tested. Using plaque forming unit assays, cell viability assays and molecular docking, we found that NQ 4 was the best antiviral compound, while AQ 11 was the most active and selective molecule on the tested tumor cells. NQ 4 showed a fair antiviral activity against Herpesviruses (EC50: <0.4 µg/mL, <1.28 µM) and DENV-2 (1.6 µg/mL, 5.1 µM) on pre-infective stages. Additionally, NQ 4 disrupted the viral attachment of HHV-1 to Vero cells (EC50: 0.12 µg/mL, 0.38 µM) with a very high selectivity index (SI = 1728). The in silico analysis predicted that this quinone could bind to the prefusion form of the E glycoprotein of DENV-2. These findings demonstrate that NQ 4 is a potent and highly selective antiviral compound, while suggesting its ability to prevent Herpes and Dengue infections. Additionally, AQ 11 can be considered of interest as a leader for the design of new anticancer agents.

In vitro and in vivo evaluation of rotary-jet-spun poly(ɛ-caprolactone) with high loading of nano-hydroxyapatite.

Herein, poly(ɛ-caprolactone) (PCL) mats with different amounts of nanohydroxyapatite (nHAp) were produced using rotary-jet spinning (RJS) and evaluated in vitro and in vivo. The mean fiber diameters of the PCL, PCL/nHAp (3%), PCL/nHAp (5%), and PCL/nHAp (20%) scaffolds were 1847 ± 1039, 1817 ± 1044, 1294 ± 4274, and 845 ± 248 nm, respectively. Initially, all the scaffolds showed superhydrophobic behavior (contact angle around of 140oC), but decreased to 80° after 30 min. All the produced scaffolds were bioactive after soaking in simulated body fluid, especially PCL/nHAp (20%). The crystallinity of the PCL scaffolds decreased progressively from 46 to 21% after incorporation of 20% nHAp. In vitro and in vivo cytotoxicity were investigated, as well as the mats' ability to reduce bacteria biofilm formation. In vitro cellular differentiation was evaluated by measuring alkaline phosphatase activity and mineralized nodule formation. Overall, we identified the total ideal amount of nHAp to incorporate in PCL mats, which did not show in vitro or in vivo cytotoxicity and promoted lamellar bone formation independently of the amounts of nHAp. The scaffolds with nHAp showed reduced bacterial proliferation. Alizarin red staining was higher in materials associated with nHAp than in those without nHAp. Overall, this study demonstrates that PCL with nHAp prepared by RJS merits further evaluation for orthopedic applications.

Biotransformation of 4-nitrophenol by co-immobilized Geobacter sulfurreducens and anthraquinone-2-sulfonate in barium alginate beads.

Geobacter sulfurreducens and anthraquinone-2-sulfonate (AQS) were used suspended and immobilized in barium alginate during the biotransformation of 4-nitrophenol (4-NP). The assays were conducted at different concentrations of 4-NP (50-400 mg/L) and AQS, either in suspended (0-400 µM) or immobilized form (0 or 760 µM), and under different pH values (5-9). G. sulfurreducens showed low capacity to reduce 4-NP in absence of AQS, especially at the highest concentrations of the contaminant. AQS improved the reduction rates from 0.0086 h-1, without AQS, to 0.149 h-1 at 400 µM AQS, which represent an increment of 17.3-fold. The co-immobilization of AQS and G. sulfurreducens in barium alginate beads (AQSi-Gi) increased the reduction rates up to 4.8- and 7.2-fold, compared to incubations with G. sulfurreducens in suspended and immobilized form, but in absence of AQS. AQSi-Gi provides to G. sulfurreducens a barrier against the possibly inhibiting effects of 4-NP.

Optimized protocol for multigram preparation of emodin anthrone, a precursor in the hypericin synthesis.

Emodin reduction to emodin anthrone comprise one of three process steps involved in the hypericin synthesis, a powerful natural photosensitiser found in plants of the genus Hypericum. In this communication, an optimized protocol was established for emodin reduction enabling an efficient multigram preparation of emodin anthrone. A screening of reducing agent (SnCl2·2H2O and HClconc) under different reaction times was employed in micro-scale and monitored by electronic absorption spectroscopy technique. Data showed lower yields of emodin anthrone when some experimental conditions previously described in the literature were reproduce. However, using the optimized protocol for the emodin reduction these yields were overcoming, and a gram-scale supply experiment was reproducible for the preparation of 10 grams of emodin anthrone with excellent yield.

Effects of photostimulation on the catabolic process of xenobiotics.

Light biotechnology is a promising tool for enhancing recalcitrant compounds biodegradation. Xenobiotics can cause a significant impact on the quality of the results achieved by sewage treatment systems due to their recalcitrance and toxicity. The optimization of bioremediation and industrial processes, aiming to increase efficiency and income is of great value. The aim of this study was to accelerate and optimize the hydrolysis of Remazol Brilliant Blue R by photo stimulating a thermophilic bacterial consortium. Three experimental groups were studied: control group; LED Group and Laser Group. The control group was exposed to the same conditions as the irradiated groups, except exposure to light. The samples were irradiated in Petri dishes with either a Laser device (λ660 nm, CW, θ = 0.04 cm2, 40 mW, 325 s, 13 J/cm2) or by a LED prototype (λ632 ±â€¯2 nm, CW, θ = 0.5 cm2, 145 mW, 44 s, 13 J/cm2). We found that, within 48-h, statistically significant differences were observed between the irradiated and the control groups in the production of RNA, proteins, as well as in the degradation of the RBBR. It is concluded that, both Laser and LED light irradiation caused increased cellular proliferation, protein production and metabolic activity, anticipating and increasing the catabolism of the RBBR. Being the economic viability a predominant aspect for industrial propose our results indicates that photo stimulation is a low-cost booster of bioprocesses.

(-)-Shikimic Acid as a Chiral Building Block for the Synthesis of New Cytotoxic 6-Aza-Analogues of Angucyclinones.

We describe the syntheses of nine new angucyclinone 6-aza-analogues, achieved through a hetero Diels-Alder reaction between the shikimic acid derivative-azadiene 13, with different naphthoquinones. The cytotoxic activity of the new synthesized compounds and five angucyclinones, previously reported, was evaluated in vitro against three cancer cell lines: PC-3 (prostate cancer), HT-29 (colon cancer), MCF-7 (breast cancer), and one non-tumoral cell line, human colon epithelial cells (CCD841 CoN). Our results showed that most 6-azadiene derivatives exhibited significant cytotoxic activities, which was demonstrated by their IC50 values (less than 10 µM), especially for the most sensitive cells, PC-3 and HT-29. From a chemical point of view, depending on the protected group of ring A and the pattern of substitution on ring D, cytotoxicity elicited these compounds, in terms of their potency and selectivity. Therefore, according to these chemical features, the most promising agents for every cancer cell line were 7a, 17, and 19c for PC-3 cells; 7a, 17, and 20 for HT-29 cells, and 19a for MCF-7 cells.

Monitoring the Activity of Immobilized Lipase with Quinizarin Diester Fluoro-Chromogenic Probe.

Quinizarin diester is used as a fluoro-chromogenic substrate of the activity of lipase supported in poly(methylmetacrylate) beads (CALB, Novozym® 435) dispersed in organic solvents. The monoester and diester of quinizarin are both non-fluorescent species contrasting with the enzymatic product quinizarin that shows optical absorption in the visible region and strong fluorescence signal. The enzymatic conversion is accomplished by spectroscopic measurements and it follows a sigmoid curve from which the mean reaction time of the enzymatic process can be determined. This parameter indicates the enzyme activity of the immobilized lipase. Its dependency with the amount of lipase allowed the determination of the ratio of the catalytic rate and the Michaelis constant (kc/Km) and the experimental value found was (1.0 ± 0.1) × 10-2 mg-1/min in the case of quinizarin diacetate.

Panus tigrinus as a potential biomass source for Reactive Blue decolorization: isotherm and kinetic study

Background: Textile and dye industries pose a serious threat to the environment. Conventional methods used for dye treatment are generally not always effective and environmentally friendly. This drove attention of scores of researchers to investigate alternative methods for the biodegradation of dyes using fungal strains. In this work, white-rot fungus (Panus tigrinus) was used as a biosorbent for the decolorization of Reactive Blue 19. The process parameters that were varied were initial concentration (50­150 mg/L), contact time (30­90 min), and pH (2­6). In addition, to gain important data for the evaluation of a sorption process, the equilibrium and kinetics of the process were determined. Results: White-rot fungus showed great potential in decolorizing Azo dyes. The strain showed the maximum decolorization of 83.18% at pH 2, a contact time of 90 min, and an initial concentration of 50 mg/L. The Langmuir isotherm described the uptake of the Reactive Blue 19 dye better than the Freundlich isotherm. Analysis of the kinetic data showed that the dye uptake process followed the pseudo second-order rate expression. Conclusion: The biosorption process provided vital information on the process parameters required to obtain the optimum level of dye removal. The isotherm study indicated the homogeneous distribution of active sites on the biomass surface, and the kinetic study suggested that chemisorption is the rate-limiting step that controlled the biosorption process. According to the obtained results, P. tigrinus biomass can be used effectively to decolorize textile dyes and tackle the pollution problems in the environment.

Photosensitizing anthraquinones from Heterophyllaea lycioides (Rubiaceae).

Seven anthraquinones were isolated from aerial parts of Heterophyllaea lycioides (Rusby) Sandwith (Rubiaceae), including three derivatives that have not been described before: a hetero-bianthraquinone identified as (R)-2-hydroxymethyl-2'methyl-1,1',6,6'-tetrahydroxy-5,5' bianthraquinone (lycionine), and two mono-chlorinated derivatives related to soranjidiol. One of them is a homo-bianthraquinone: (R)-7-chloro-2,2'-dimethyl-1,1',6,6'-tetrahydroxy-5,5' bianthraquinone (7-chlorobisoranjidiol), whereas the second halogenated derivative corresponds to a monomeric structure: 5-chloro-1,6-dihydroxy-2-methyl anthraquinone (5-chlorosoranjidiol). The four known compounds were already isolated from another species of this genus, H. pustulata, and they were identified as 5,5'-bisoranjidiol, soranjidiol, pustuline and heterophylline. Structural elucidation was performed by means of an extensive spectroscopic analysis, including 1D and 2D NMR data as well as by HRMS analysis. Chemical structures of 7-chlorobisoranjidiol and 5-chlorosoranjidiol were confirmed by their synthesis from 5,5'-bisoranjidiol and soranjidiol, respectively. Type I photosensitizing properties (superoxide anion radical generation, O2-) were assessed by using the nitroblue tetrazolium assay. When lycionine and chlorinated derivatives were irradiated, they enhanced the O2- production with respect to the control; 7-chlorobisoranjidiol stood out by generating an increase of 20%, whereas the other anthraquinones only produced a slight increase of 7%.