Novel emissive styryl dyes from 9-methoxy anthracene: Synthesis, photophysical, thermal stability, viscosity, and DFT study.

Novel styryl colorants based on anchoring methoxy with anthracene as a donor linked with various active methylene acceptor groups to derive a conjugated π-system along with push-pull geometry were synthesized and well characterized. Photophysical properties were studied in different polarity solvents. The impact of solvent polarizability is delivered in redshifts in absorption and emission spectra, in addition to enhancing the quantum yield. The benzoxazole and benzimidazole moieties in 4c and 4d demonstrated heat stability of more than 300 °C. Fluorescent intensity is directly proportional to the viscosity and 4a demonstrates a notable viscosity sensor through 1.36 fold increase in intensity. In comparison to other styryl dyes, 4c and 4d were shown to have higher values in DMSO for polarizability (53.3496 × 10-24 esu and 53.7459 × 10-24 esu) and first-order hyperpolarizability (86.3467 × 10-30 esu and 89.1941 × 10-30 esu) as well as second-order hyperpolarizability (1768.9121 × 10-36 esu and 1740.6940 × 10-36 esu) due to presence of heterocyclic character. NLO properties of all the styryl dyes 4a-4e are within the fundamental boundary limits. The 4d (benzoxazole) dye exhibited a small HOMO-LUMO energy gap of 2.8825 eV, whereas the 4b and 4e dyes had a larger band gap due to the presence of a carbonyl group.

Fluorescence and Photophysical Properties of Anthracene and Phenanthrene in Water.

Polyaromatic hydrocarbons (PAHs) are widely spread pollutants in the environment, including soil and water. Anthracene (anth) and phenanthrene (phen) pose severe health impacts on human lives due to their carcinogenic nature by increasing cancer risk to the skin, lungs, and bladder. Fluorescence spectroscopy is a promising , efficient and straightforward tool for characterizing these trace PAHs in water. Therefore, the current work provides a detailed insight into the fluorescence properties of anth and phen in water. The fluorescence EEMs (excitation-emission matrices) of anth showed emissions at 380 nm, 400 nm, and 425 nm with single excitation at 250 nm, whereas phen showed two emissions < 380 nm, at 350 nm and 365 with single excitation at 250 nm. Then the theoretical EX/EM wavelengths were calculated by DFT and CIS-B3LYP for these compounds in water. The environmental effect of pH variation on fluorescence EEM shows a significant difference in fluorescence intensity without changing in peak locations, with highest fluorescence intensity at neutral pH than acidic and alkaline. Furthermore, the theoretical pH effect was described for the first time by simulating the protonated (+ 1), deprotonated (-1) and neutral molecules in water at the DFT level of theory. The variation in simulated oscillator strengths was similar in trend with the experimental fluorescence intensity of these compounds. The HOMO-LUMO were calculated to obtain the energy gap, molecular softness, molecular hardness, electronic potential and electrophilicity of anth and phen. To find the fluorophore contribution, the fluorescence of homogeneous mixture of both isomers was analyzed, which showed an enhanced fluorescence intensity of anth by 12-20%, whereas a decrease of 9-14% was observed in phen. This study describes that the fluorescence technique could be a fast and easy method to distinguish and identify PAHs isomers (anth and phen) in water.

[1-(Anthracen-9-ylmeth-yl)-1,4,7,10-tetra-aza-cyclododeca-ne]chlorido-zinc(II) nitrate.

In the title salt, [ZnCl(C23H30N4)]NO3, the central ZnII atom of the complex cation is coordinated in a square-pyramidal arrangement by four nitro-gen atoms from cyclen (1,4,7,10-tetra-aza-cyclo-dodeca-ne) in the basal plane and one chlorido ligand in the apical position. The anthracene group attached to cyclen contributes to the crystal packing through inter-molecular T-shaped π inter-actions. Additionally, the nitrate anion participates in inter-molecular N-H⋯O hydrogen bonds with cyclen.

Anthracene-Induced Alterations in Liverwort Architecture In Vitro: Potential for Bioindication of Environmental Pollution.

Polycyclic aromatic hydrocarbons (PAHs) are widespread globally, primarily due to long-term anthropogenic pollution sources. Since PAHs tend to accumulate in soil sediments, liverwort plants, such as Lunularia cruciata, are susceptible to their adverse effects, making them good models for bioindicators. The aim of this study was to probe the impact of anthracene, a three-ring linear PAH, on the growth parameters of L. cruciata and the relationship established with the internalization of the pollutant throughout the phenology of the plant. Intrinsic plant responses, isolated from external factors, were assessed in vitro. L. cruciata absorbed anthracene from the culture medium, and its bioaccumulation was monitored throughout the entire process, from the gemma germination stage to the development of the adult plant, over a total period of 60 days. Consequently, plants exposed to concentrations higher than 50 µM anthracene, decreased the growth area of the thallus, the biomass and number of tips. Moreover, anthracene also impinged on plant symmetry. This concentration represented the maximum limit of bioaccumulation in the tissues. This study provides the first evidence that architectural variables in liverwort plants are suitable parameters for their use as bioindicators of PAHs.

Near-IR Emissive B-N Lewis Pair-Functionalized Anthracenes via Selective LUMO Extension in Conjugated Dimer and Polymer.

Acenes are attractive as building blocks for low gap organic materials with applications, for example, in organic light emitting diodes, solar cells, bioimaging and diagnostics. Previously, we have shown that modification of dipyridylanthracene via B-N Lewis pair fusion (BDPA) strongly redshifts the emission, while facilitating self-sensitized reactivity toward O2 to reversibly generate the corresponding endoperoxides. Herein, we report on the further expansion of the π-system of BDPA to a vinyl-substituted monomer, vinylene-bridged dimer, and a polymer with an average of 20 chromophores. The extension of π-conjugation results in largely reduced band gaps of 1.8 eV for the dimer and 1.7 eV for the polymer, the latter giving rise to NIR emission with a maximum at 731 nm and an appreciable quantum yield of 7 %. Electrochemical and computational studies reveal efficient delocalization of the lowest unoccupied molecular orbital (LUMO) along the pyridyl-anthracene-pyridyl axis, which results in effective electronic communication between BDPA units, selectively lowers the LUMO, and ultimately narrows the band gap. Time-resolved emission and transient absorption (TA) measurements offer insights into the pertinent photophysical processes. Extension of π-conjugation also slows down the self-sensitized formation of endoperoxides, while significantly accelerating the thermal release of singlet oxygen to regenerate the parent acenes.

Toggling the Oxygen Affinity between Anthracenes and Naphthalenes.

We present the design of an anthracenyl⎯naphthyl (ANT⎯NAPH) dyad and its application as a luminescent 4-stage photo switch. Both segments can individually react with singlet oxygen to switch off an optical response. In their initial form the larger ANT component reacts significantly faster and thus an ANTO2⎯NAPH stage is turned on, observed by optical response of the remaining NAPH. To reduce its reactivity, ANT is substituted with two pyridine rings. This concept is first investigated and quantified on ANT and NAPH as separated molecules. Upon protonation the reaction of ANT becomes significantly slower. For the three possible pyridyl isomers this effect increases along the order meta

Amphiphilic Single-Chain Polymer Nanoparticles as Imaging and Far-Red Photokilling Agents for Photodynamic Therapy in Zebrafish Embryo Xenografts.

This work introduces rationally designed, improved amphiphilic single-chain polymer nanoparticles (SCNPs) for imaging and photodynamic therapy (PDT) in zebrafish embryo xenografts. SCNPs are ultrasmall polymeric nanoparticles with sizes similar to proteins, making them ideal for biomedical applications. Amphiphilic SCNPs result from the self-assembly in water of isolated synthetic polymeric chains through intrachain hydrophobic interactions, mimicking natural biomacromolecules and, specially, proteins (in size and when loaded with drugs, metal ions or fluorophores also in function). These ultrasmall, soft nanoparticles have various applications, including catalysis, sensing, and nanomedicine. Initial in vitro experiments with nonfunctionalized, amphiphilic SCNPs loaded with a photosensitizing Zn phthalocyanine with four nonperipheral isobutylthio substituents, ZnPc, showed promise for PDT. Herein, the preparation of improved, amphiphilic SCNPs containing ZnPc as highly efficient photosensitizer encapsulated within the nanoparticle and surrounded by anthracene units is disclosed. The amount of anthracene groups and ZnPc molecules within each single-chain nanoparticle controls the imaging and PDT properties of these nanocarriers. Critically, this work opens the way to improved PDT applications based on amphiphilic SCNPs as a first step toward ideal, long-term artificial photo-oxidases (APO).

Fluorescence lifetime nanothermometer based on the equilibrium formation of anthracene AIE-excimers in living cells.

The effective measurement of temperature in living systems at the nano and microscopic scales continues to be a challenge to this day. Here, we study the use of 2-(anthracen-2-yl)-1,3-diisopropylguanidine, 1, as a nanothermometer based on fluorescence lifetime measurements and its bioimaging applications. In aqueous solution, 1 is shown in aggregated form and the equilibrium between the two main aggregate types (T-shaped and π-π) is highly sensitive to the temperature. The heating of the medium shifts the equilibrium toward the formation of highly emissive T-shaped aggregates. This species shows a high fluorescence emission and a long lifetime in comparison with the π-π aggregates and the freé monomer. A linear relationship between the fluorescence lifetime and the temperature both in aqueous solution and in a synthetic intracellular buffer was found. Fluorescence lifetime imaging microscopy (FLIM) also showed a linear relationship between lifetime and temperature with an excellent sensitivity in MCF7 breast cancer cells, which opens the door for its potential use as FLIM nanothermometer in the biomedical field.

Anthracene detoxification by Laccases from indigenous fungal strains Trichoderma lixii FLU1 and Talaromyces pinophilus FLU12.

The persistence and ubiquity of polycyclic aromatic hydrocarbons (PAHs) in the environment necessitate effective remediation strategies. Hence, this study investigated the potential of purified Laccases, TlFLU1L and TpFLU12L, from two indigenous fungi Trichoderma lixii FLU1 (TlFLU1) and Talaromyces pinophilus FLU12 (TpFLU12), respectively for the oxidation and detoxification of anthracene. Anthracene was degraded with vmax values of 3.51 ± 0.06 mg/L/h and 3.44 ± 0.06 mg/L/h, and Km values of 173.2 ± 0.06 mg/L and 73.3 ± 0.07 mg/L by TlFLU1L and TpFLU12L, respectively. The addition of a mediator compound 2,2-azino-bis (3-ethylbenzothiazoline-6-sulfonic acid) (ABTS) to the reaction system significantly increased the degradation of anthracene, with up to a 2.9-fold increase in vmax value and up to threefold decrease in Km values of TlFLU1L and TpFLU12L. The GC-MS analysis of the metabolites suggests that anthracene degradation follows one new pathway unique to the ABTS system-hydroxylation and carboxylation of C-1 and C-2 position of anthracene to form 3-hydroxy-2-naphthoic acid, before undergoing dioxygenation and side chain removal to form chromone which was later converted into benzoic acid and CO2. This pathway contrasts with the common dioxygenation route observed in the free Laccase system, which is observed in the second degradation pathways. Furthermore, toxicity tests using V. parahaemolyticus and HT-22 cells, respectively, demonstrated the non-toxic nature of Laccase-ABTS-mediated metabolites. Intriguingly, analysis of the expression level of Alzheimer's related genes in HT-22 cells exposed to degradation products revealed no induction of neurotoxicity unlike untreated cells. These findings propose a paradigm shift for bioremediation by highlighting the Laccase-ABTS system as a promising green technology due to its efficiency with the discovery of a potentially less harmful degradation pathway, and the production of non-toxic metabolites.

A series of anthracene-derived dyes for Cu2+-assisted CO sensing and bio-imaging: synthesis, performance, and mechanism.

Endogenous CO acts as an important messenger for signal transduction and therapeutic effect in the human body. Fluorescent imaging appears to be a promising method for endogenous CO recognition, but traditional luminescent probes based on Pd-complexes suffered from defects of high cost. In this work, four anthracene-derived dyes having an = N-N = group were synthesized for Cu2+-assisted CO sensing. Their molecular structure, photophysical performance and spectral response to Cu2+ and CO were analyzed in detail. The optimal probe showed good selectivity and quenching effect to Cu2+, with PLQY (photoluminescence quantum yield) decreased from 0.33 to 0.04. The quenching mechanism was found as a static quenching mechanism by forming a non-fluorescent complex with Cu2+ (stoichiometric ratio = 1:1), as revealed by single crystal, EPR (electron paramagnetic resonance), and XPS (X-ray photoelectron spectroscopy) analysis. Such quenching effect could be reversed by CO, showing recovered fluorescence, with PLQY recovered to 0.32 within 328 s. Discussion on cellular endogenous CO imaging was included as well.

Carbohydrate-Functionalized Anthracene Carboximides as Multivalent Ligands and Bio-Imaging Agents.

Anthracene carboximides (ACIs) conjugated with gluco-, galacto- and mannopyranosides are synthesized, by glycosylation of N-hydroxyethylanthracene carboximide acceptor with glycosyl donors. Glycoconjugation of anthracene carboximide increases the aq. solubility by more than 3-fold. The glycoconjugates display red-shifted absorption and emission, as compared to anthracene. Large Stokes shift (λabs/λem=445/525 nm) and high fluorescence quantum yields (Φ) of 0.86 and 0.5 occur in THF and water, respectively. The ACI-glycosides undergo facile photodimerization in aqueous solutions, leading to the formation of the head-to-tail dimer, as a mixture of syn and anti-isomers. Solution phase and solid-state characterizations by dynamic light scattering (DLS), microscopic imaging by atomic force (AFM) and transmission electron (TEM) microscopies reveal self-assembled vesicle structures of ACI glycosides. These self-assembled structures act as multivalent glycoclusters for ligand-specific lectin binding, as evidenced by the binding of Man-ACI to Con A, by fluorescence and turbidity assays. The conjugates do not show cellular cytotoxicity (IC50) till concentrations of 50 µM with HeLa and HepG2 cell lines and are cell-permeable, showing strong fluorescence inside the cells. These properties enable the glycoconjugates to be used in cell imaging. The non-selective cellular uptake of the glycoconjugates suggests a passive diffusion through the membrane.

Axial Coordinated Manganese(III) Porphyrin/Tetraazaporphyrin - 4-(10-phenylanthracen-9-yl)Pyridine Dyads: Self-Assembly, Structure and Spectral Properties in Ground and Excited States.

Self-assembly of new donor-acceptor systems based on (5,10,15,20-tetraphenylporphinato)manganese(III)/(5,10,15,20-tetra-4-tert-butylphenylporphinato)manganese(III)/(octakis(4-tert-butylphenyl)tetraazaporphinato)manganese(III) acetate ((AcO)MnTPP/(AcO)MnTBPP/(AcO)MnTAP) and 4-(10-phenylanthracen-9-yl)pyridine (PyAn) was studied using fluorescence spectroscopy and mass spectrometry. It was found that the coordination complexes of 1 : 1 composition (dyads) are formed in toluene. The spectral properties, the chemical structures and redox behavior of the dyads were described using 1H NMR, IR, ESR spectroscopy and cyclic voltammetry, respectively. The dynamic processes and the characteristics in the excited state of the dyads were obtained using the femtosecond transient absorption spectroscopy method. Density functional theory (DFT), time-dependent DFT methods were used to elucidate the dyad electronic structures and to establish the differences in their frontier molecular orbitals. The analysis of the lambda parameter and the distance of hole-pair interaction was indicated more favorable charge transfer between the macrocycle and the axial PyAn fragment in (AcO)(PyAn)MnTAP. The calculated values of the zero-field splitting parameters D and E/D, together with the g tensors of the lowest spin-orbit state for (AcO)MnTPP and (AcO)(PyAn)MnTPP were obtained using the combination of DFT and Multireference Perturbation Theory (CASSCF/NEVPT2) simulations. The data obtained develop the fundamental basis in the field of photovoltaics and show the prospects for the study of molecular systems of this class.

Dissecting the long-term neurobehavioral impact of embryonic benz[a]anthracene exposure on zebrafish: Social dysfunction and molecular pathway activation.

Benz[a]anthracene (BaA), a prevalent environmental contaminant within the polycyclic aromatic hydrocarbon class, poses risks to both human health and aquatic ecosystems. The impact of BaA on neural development and subsequent social behavior patterns remains inadequately explored. In this investigation, we employed the zebrafish as a model to examine the persisting effects of BaA exposure on social behaviors across various developmental stages, from larvae, juveniles to adults, following embryonic exposure. Our findings indicate that BaA exposure during embryogenesis yields lasting neurobehavioral deficits into adulthood. Proteomic analysis highlights that BaA may impair neuro-immune crosstalk in zebrafish larvae. Remarkably, our proteomic data also hint at the activation of the aryl hydrocarbon receptor (AHR) and cytochrome P450 1A (CYP1A) pathway by BaA, leading to the hypothesis that this pathway may be implicated in the disruption of neuro-immune interactions, contributing to observable behavioral disruptions. In summary, our findings suggest that early exposure to BaA disrupts social behaviors, such as social ability and shoaling behaviors, from the larval stage through to maturity in zebrafish, potentially through the detrimental effects on neuro-immune processes mediated by the AHR-CYP1A pathway.

Photodegradation enhances the toxic effect of anthracene on skin.

Anthracene, a polycyclic aromatic hydrocarbon (PAH), is a widespread environmental pollutant that poses potential risks to human health. Exposure to anthracene can result in various adverse health effects, including skin-related disorders. Photo exposure sufficiently removes the anthracene from the environment but also generates more degradation products which can be more toxic. The goal of this study was to assess the change in anthracene dermotoxicity caused by photodegradation and understand the mechanism of this change. In the present study, over 99.99% of anthracene was degraded within 24 h of sunlight exposure, while producing many intermediate products including 9,10-anthraquinone and phthalic acid. The anthracene products with different durations of photo exposure were applied to 2D and 3D human keratinocyte cultures. Although the non-degraded anthracene significantly delayed the cell migration, the cell viability and differentiation decreased dramatically in the presence of the photodegraded anthracene. Anthracene photodegradation products also altered the expression patterns of a number of inflammation-related genes in comparison to the control cells. Among these genes, il1a, il1b, il8, cxcl2, s100a9, and mmp1 were upregulated whereas the tlr4 and mmp3 were downregulated by the photodegraded anthracene. Topical deliveries of the photodegraded and non-degraded anthracene to the dorsal skin of hairless mice showed more toxic effects by the photodegraded anthracene. The 4-hour photodegradation products of anthracene thickened the epidermal layer, increased the dermal cellularity, and induced the upregulation of inflammatory markers, il1a, il1b, s100a9, and mmp1. In addition, it also prevented the production of a gap junction protein, Connexin-43. All the evidence suggested that photodegradation enhanced the toxicities of anthracene to the skin. The 4-hour photodegradation products of anthracene led to clinical signs similar to acute inflammatory skin diseases, such as atopic and contact dermatitis, eczema, and psoriasis. Therefore, the potential risk of skin irritation by anthracene should be also considered when an individual is exposed to PAHs, especially in environments with strong sunlight.

Investigation of the photolysis process of benzo(a)anthracene (BaA) on polyvinyl chloride (PVC) and polystyrene (PS) microplastics: Plastics aging effect, transformation products and toxicity assessment.

Microplastics (MPs) and persistent pollutants (POPs) are new pollutants that are extensively studied worldwide. To fill the gaps that the degradation processes and mechanisms of polycyclic aromatic hydrocarbons (PAHs) on the surface of most MPs are still unclear, the photochemical transformation of benzo(a)anthracene (BaA) on polyvinyl chloride (PVC) MPs and polystyrene (PS) MPs in water were investigated and compared. The photolysis of BaA on the surface of PS in water proceeded easier than that on PVC within the 48 h irradiation period, with the pseudo-first-order rate constant of 0.0489 min-1 and 0.0181 min-1, respectively, which can be ascribed to the smaller particle size and more OH production of PS MPs. Due to the light competition between the chromophore and BaA as well as the light-shielding effect, aged MPs showed an inhibitory effect on the degradation of BaA compared with pristine MPs. For BaA/PVC MPs system, the degradation of BaA in real water was not significantly affected by coexisting ions and humic acid (HA) (p < 0.05), while slight inhibitory effect on the degradation of BaA appeared for PS MPs in different water matrices (UP: 86.97 %, YR: 84.47 %, PR: 81.42 % and HR: 83.21 %). According to the electron paramagnetic resonance (EPR) test, quenching experiment and probe experiment, the relative contribution of direct photolysis (PVC: 82.02 %; PS: 69.54 %) and indirect photolysis (PVC: 17.98 %; PS: 30.46 %) was confirmed. A total of 14 products were identified, and the product types were not affected by plastics aging. The results of the toxicity assessment indicated that although some intermediate products remained toxic to aquatic organisms, the toxicity of most products was lower than that of BaA. This study provides new insights into the environmental fate of PAHs and the role of MPs in the photolysis process of contaminants in surface water.

Effect of Ambrosia arborescens Mill. ethanolic extract on breast cancer induced in rats.

Background and Aims: Ambrosia arborescens Mill. (A. arborescens) is an aromatic plant used in traditional medicine as an anti-inflammatory, anti-tussive, anti-rheumatic, and anti-diarrheal agent. This study aimed to evaluate the effect of A. arborescens Mill. on a Rattus norvegicus var. albinus-induced breast cancer model. Materials and Methods: We collected A. arborescens from the province of Julcán, La Libertad Region, Per, and prepared an ethanolic extract using pulverized leaves macerated in 96° ethanol for 72 h with magnetic stirring. In the evaluation of anticancer activity, four experimental groups with 10 female rats each were formed: Group I (Control-7,12-dimethylbenz[a]anthracene [DMBA]), which received DMBA (single dose) and physiological saline solution for 4 months, and Groups II, III, and IV, which received DMBA (single dose) and 200, 400, and 600 mg/kg/day of the ethanolic extract of A. arborescens, respectively, for 4 months. Results: The DMBA control group presented histological characteristics of ductal carcinoma in situ with necrotic and inflammatory areas, whereas the A. arborescens extract group showed a decrease in tumor volume and recovery of the ductal duct. Conclusion: Ethanol extract of A. arborescens leaves decreases tumor development in rats with induced breast cancer, and this effect is dose-dependent.

Novel Anthracene and Carbazole Based Aggregation Induced Enhanced Emission Active Schiff Base as a Selective Sensor for Cu2+ ions.

In present work our group has synthesized two novel Schiff-bases, Di-Carbazole based Schiff-base (DB-1) and Di-Anthracene based Schiff-base (DB-2) using condensation reaction and characterized thorough different spectroscopic techniques such as mass spectrometry, IR spectroscopy, 1H and 13C NMR spectroscopy. Furthermore, the AIE(Aggregation induced emission) studies were done using water-THF mixture. As compared to pure THF, the DB-2 showed a 17.8-fold increase in fluorescence intensity with a bathochromic shift of 64 nm in 80% water: THF mixture. For DB-1increase was seen at 70% water-THF combination. The analysis of the dynamic light scattering (DLS) further supported this excellent AIEE (Aggregation induced enhanced emission) characteristic. Furthermore, the spectrofluorometric techniques were used to examine the capacity of both Schiff bases to detect the heavy metals. It was discovered that only DB-1, with a detection limit of 2.4 × 10-8 M, was selective for the Cu2+ ion, whereas DB-2 had no sensing capability for metal ions. The Job's plot was used to determine the stoichiometry ratio of the DB-1 with Cu2+ to further examine the process. It was discovered that the ratio was 1:1 (DB-1:Cu2+). Additionally, the association constant of DB-1 for Cu2+ was 5.1 × 1011 M-1, demonstrating the excellent binding affinity of DB-1 for the Cu2+ ion.

Low Dose of Nickel and Benzo [a] Anthracene in Rat-Diet, Induce Apoptosis, Fibrosis, and Initiate Carcinogenesis in Liver via NF-Æ˜ß Pathway.

Environmental contaminants such as polycyclic aromatic hydrocarbon (PAH) and heavy metals are major contaminants of food such as fish thus serving as source of exposure to human. This study was designed to evaluate the carcinogenic risk and other risks associated with long-term consumption of environmentally relevant dose of nickel and benzo [a] anthracene in rats. Thirty-six (36) male rats weighing between 80 and 100 g were assigned into 6 groups of 6 animals each; normal, nickel-, and benzo [a] anthracene-exposed groups for 12 and 24 weeks, respectively. Micronucleus and comet analyses were done in the blood, liver, and bone marrow. Liver function, redox, and inflammatory markers (AST, ALT, GGT, SOD, GSH, MDA, protein carbonyl, protein thiol, total protein, IL-10, 1L-1ß, TNF-α, TGF-ß NF-Ƙß, and 8-oxodeoxyguansine) were analysed by standard methods. Immuno-histochemical quantification of Bax, Bcl2, and Erk 1/2 as well as mRNA expression of cyclin D1 was done in liver. From the results, weight gain was observed in varying degrees throughout the exposure period. The polychromatic erythrocytes/normochromatic erythrocytes ratio > 0.2 indicates no cytotoxic effects on the bone marrow. Percentage-MnPCE in blood significantly (p < 0.05) increased throughout exposure duration. Percentage tail DNA in blood was significantly (< 0.05) increased at weeks 20 and 24 in the exposed groups and in liver at weeks 12 (16.22 ± 0.47) and 24 (17.00 ± 0.36) of nickel-exposed rats. The aspartate amino transferase (AST):alanine amino transferase (ALT) ratio indicated fatty liver disease in the benzo [a] anthracene (0.90) and acute liver injury in the nickel (> 10 times greater than the upper limits of the reference group) exposed groups during the first 12 weeks. Observation from the histological and cytological data of the liver revealed the presence of inflammation, fibrosis, and high nuclear/cytoplasmic ratio, respectively, in the nickel and benzo [a] anthracene groups. Only benzo [a] anthracene induced liver oxidative stress with significant (p < 0.05) decrease in SOD (0.64 ± 0.02) activity and increase in protein carbonyl (7.60 ± 0.80 × 10-5) and MDA (57.10 ± 6.64) concentration after 24 weeks. Benzo [a] anthracene up-regulated the cyclin D1 expression and significantly (p < 0.05) increased the levels of the cytokines. Nickel and benzo [a] anthracene significantly (p < 0.05) increased the Bax (183.45 ± 6.50 and 199.76 ± 10.04) and Erk 1/2 (108.25 ± 6.41 and 136.74 ± 4.22) levels when compared with the control (37.43 ± 22.22 and 60.37 ± 17.86), respectively. Overall result showed that the toxic effects of nickel and benzo [a] anthracene might involve fibrosis, cirrhosis, apoptosis, and inflammation of the liver. As clearly demonstrated in this study, benzo [a] anthracene after the 24 weeks of exposure stimulates carcinogenic process by suppressing the liver antioxidant capacity, altering apoptotic, cell proliferation, and differentiation pathways.

Dietary supplementation with seeds of Sesamum indicum L. (pedaliaceae) mitigates the 7,12-dimethylbenz(a)anthracene-induced breast tumor burden in rats.

OBJECTIVES: Sesamum indicum L. seeds; rich in zinc and lignans are endowed with antioxidant and immunomodulatory properties which attract research on their anticancer potential. Although many studies have reported the in vitro antitumor potential of S. indicum and its phytoconstituents, much is yet to be known about its in vivo effects. To fill this gap, the effects of dietary supplementation with seeds of S. indicum in 7,12-dimethylbenz(a)anthracene-exposed rats was assessed. METHODS: 42 rats aged 30-35 days were randomized into six groups (n=6) as follows: the normal (NOR) and negative (DMBA) control groups were fed with standard diet; the positive control group (DMBA + Zinc) was fed with standard diet supplemented with commercial zinc (0.01 %); the test groups were fed with standard diet supplemented with S. indicum seeds in different proportions (6.25 , 12.5 and 25 %). Breast cancer was induced by a single administration of DMBA (50 mg/kg BW, s.c.) diluted in corn oil. The experiment lasted 20 weeks and afterward, tumor incidence; tumor burden, tumor volume, tumor micro-architecture and some biochemical parameters were evaluated. RESULTS: As salient result, 100 % of rats in the DMBA group developed tumors, while rats feed with rat chow supplemented with S. indicum seeds (25 %) had a reduced incidence of tumors (33.3 %) and tumor volume (2.71 cm3 in sesame 25 % vs. 4.69 cm3 in the DMBA group, p˂0.01). The seeds (25 %) also slowed DMBA-induced neoplasm expansion in mammary ducts as compared to rats of DMBA group. CONCLUSIONS: In summary, supplementation with S. indicum seeds slowed breast tumorigenesis via its antioxidant capacity.

Phase Diagrams of Anthracene Derivatives in Pyridinium Ionic Liquids.

Crystal engineering for single crystallization of π-conjugated molecules has attracted much attention because of their electronic, photonic, and mechanical properties. However, reproducibility is a problem in conventional printing techniques because control of solvent evaporation is difficult. We investigated the phase diagrams of two anthracene derivatives in synthesized ionic liquids for non-volatile crystal engineering to determine the critical points for nucleation and crystal growth. Anthracene and 9,10-dibromoanthracene were used as representative π-conjugated molecules that form crystal structures with different packing types. Ionic liquids with an alkylpyridinium cation and bis(fluorosulfonyl)amide were good solvents for the anthracene derivatives from ca. 0 °C to 200 °C. The solubilities (critical points for crystal growth) of the anthracene derivatives in the ionic liquids reached the 100 mM level, which is similar to those in organic solvents. Ionic liquids with phenyl and octyl groups tended to show high-temperature dependence (a high dissolution entropy) with 9,10-dibromoanthracene. The precipitation temperature (critical point for crystal nucleation) at each 9,10-dibromoanthracene concentration was lower than the dissolution temperature. The differences between the dissolution and precipitation temperatures (supersaturated region) in the ionic liquids were greater than those in an organic solvent.