ABSTRACT
Multiphoton excitation promises opportunities for opening new photochemical reaction pathways and controlling photoproduct distributions. We demonstrate photonic control of the 6π photocyclization of ortho-terphenyl to make 4a,4b-dihydrotriphenylene (DHT). Using pump-repump-probe spectroscopy we show that 1 + 1' excitation to a high-lying reactant electronic state generates a metastable species characterized by a red absorption feature that accompanies a repump-induced depletion in the one-photon trans-dihydro product (trans-DHT); signatures of the new photoproduct are clearer for a structural analogue of the reactant that is sterically inhibited against one-photon cyclization. Quantum-chemical computations support assignment of this species to cis-DHT, which is accessible photochemically along a disrotatory coordinate from high-lying electronic states reached by 1 + 1' excitation. We use time-resolved spectroscopy to track photochemical dynamics producing cis-DHT. In total, we demonstrate that selective multiphoton excitation opens a new photoreaction channel in these photocyclizing reactants by taking advantage of state-dependent correlations between reactant and product electronic states.
Subject(s)
Chrysenes/chemistry , Light , Cyclization , Isomerism , Photons , Quantum Theory , SpectrophotometryABSTRACT
A 2D CuNi metal-organic framework (MOF) named CuxNi3-x(HHTP)2 was synthesized with 2,3,6,7,10,11-hexahydroxytriphenylene (HHTP) as the linker and was used as a sensitive scaffold to adsorb aptamer strands for the electrochemical detection of living C6 glioma cells and one of their biomarkers, epidermal growth factor receptor (EGFR). Different from conventional MOFs, the CuxNi3-x(HHTP)2 MOF comprises long-range delocalized electrons, a graphene-analog nanostructure, multiple metal states (Cu0/Cu+/Cu2+ and Ni2+/Ni3+), and abundant oxygen vacancies. With these features, the CuxNi3-x(HHTP)2 MOF anchored a large amount of C6 cell-targeted aptamer strands via coordination among metal centers, oligonucleotides, π-π stacking, and van der Waals force. The CuxNi3-x(HHTP)2-based cytosensor showed a low limit of detection (LOD) of 21 cells mL-1 toward C6 glioma cells within a wide range from 50 cells mL-1 to 1 × 105 cells mL-1. Moreover, the proposed aptasensor displayed high selectivity, good stability, acceptable reproducibility, and a low LOD of 0.72 fg mL-1 for detecting EGFR with the concentration ranging from 1 fg mL-1 to 1 ng mL-1. The aptasensor based on the CuxNi3-x(HHTP)2 MOF exhibited superior sensing performance over those based on its monometallic analogues such as Cu3(HHTP)2 MOF and Ni3(HHTP)2 MOF. Hence, this sensing strategy based on a bimetallic semiconducting MOF shows great potential for cancer diagnosis.
Subject(s)
Aptamers, Nucleotide/chemistry , Biosensing Techniques/methods , Brain Neoplasms/diagnosis , Glioma/diagnosis , Metal-Organic Frameworks/chemistry , Cell Line, Tumor , Chrysenes/chemistry , Copper/chemistry , Electrochemical Techniques/methods , ErbB Receptors/analysis , Humans , Nickel/chemistry , SemiconductorsABSTRACT
At the moment, there are no U.S. Food and Drug Administration (U.S. FDA)-approved drugs for the treatment of COVID-19, although several antiviral drugs are available for repurposing. Many of these drugs suffer from polymorphic transformations with changes in the drug's safety and efficacy; many are poorly soluble, poorly bioavailable drugs. Current tools to reformulate antiviral APIs into safer and more bioavailable forms include pharmaceutical salts and cocrystals, even though it is difficult to classify solid forms into these regulatory-wise mutually exclusive categories. Pure liquid salt forms of APIs, ionic liquids that incorporate APIs into their structures (API-ILs) present all the advantages that salt forms provide from a pharmaceutical standpoint, without being subject to solid-state matter problems. In this perspective article, the myths and the most voiced concerns holding back implementation of API-ILs are examined, and two case studies of API-ILs antivirals (the amphoteric acyclovir and GSK2838232) are presented in detail, with a focus on drug property improvement. We advocate that the industry should consider the advantages of API-ILs which could be the genesis of disruptive innovation and believe that in order for the industry to grow and develop, the industry should be comfortable with a certain element of risk because progress often only comes from trying something different.
Subject(s)
Acyclovir/chemistry , Antiviral Agents/chemistry , Betacoronavirus/drug effects , Butyrates/chemistry , Chrysenes/chemistry , Coronavirus Infections/drug therapy , Pneumonia, Viral/drug therapy , Acyclovir/pharmacology , Antiviral Agents/pharmacology , Biological Availability , Butyrates/pharmacology , COVID-19 , Chemistry, Pharmaceutical/methods , Chrysenes/pharmacology , Drug Repositioning/methods , Humans , Ionic Liquids/chemistry , Pandemics , Pentacyclic Triterpenes , SARS-CoV-2 , Solubility , COVID-19 Drug TreatmentABSTRACT
6-Nitrochrysene (6-NC) is a potent mutagen in bacteria and carcinogenic in animals. It is the most potent carcinogen ever tested in newborn mouse assay. DNA lesions resulting from 6-NC modification are likely to induce mutations if they are not removed by cellular defense pathways prior to DNA replication. Earlier studies showed that 6-NC-derived C8-2'-deoxyadenosine adduct, N-(dA-8-yl)-6-AC, is very slowly repaired in human cells. In this study, we have investigated replication of N-(dA-8-yl)-6-AC in human embryonic kidney (HEK 293T) cells and the roles of translesion synthesis (TLS) DNA polymerases in bypassing it. Replication of a plasmid containing a single site-specific N-(dA-8-yl)-6-AC adduct in HEK 293 T cells showed that human DNA polymerase (hPol) η and hPol κ played important roles in bypassing the adduct, since TLS efficiency was reduced to 26 % in the absence of these two polymerases compared to 83 % in polymerase-competent HEK 293T cells. The progeny from HEK 293T cells provided 12.7 % mutants predominantly containing AâT transversions. Mutation frequency (MF) was increased to 17.8 % in hPol η-deficient cells, whereas it was decreased to 3.3 % and 3.9 % when the adduct containing plasmid was replicated in hPol κ- and hPol ζ-deficient cells, respectively. The greatest reduction in MF by more than 90 % (to MF 1.2 %) was observed in hPol ζ-knockout cells in which hPol κ was knocked down. Taken together, these results suggest that hPol κ and hPol ζ are involved in the error-prone TLS of N-(dA-8-yl)-6-AC, while hPol η performs error-free bypass.
Subject(s)
Chrysenes/chemistry , DNA Adducts/metabolism , DNA Repair , DNA-Binding Proteins/metabolism , DNA-Directed DNA Polymerase/metabolism , Deoxyadenosines/chemistry , DNA Adducts/chemistry , DNA Replication , HEK293 Cells , HumansABSTRACT
A new 2,7,10,15-tetraethynyldibenzo[g,p]chrysene ligand (1) and two tetranuclear gold(I) derivatives containing PPh3 (3) and PMe3 (4) phosphines were synthesized and characterized by 1H and 31P NMR, IR spectroscopy, and high-resolution mass spectrometry. The compounds were studied in order to analyze the effect of the introduction of gold(I) on the supramolecular aggregation and photophysical properties. Absorption and emission spectra displayed broad bands due to the establishment of π π interactions as an indication of intermolecular contacts and the formation of aggregates. A decrease of the recorded quantum yield (QY) of the gold(I) derivatives was observed compared to the uncomplexed ligand. The introduction of the complexes into poly methyl methacrylate (PMMA) and Zeonex 480R matrixes was analyzed, and an increase of the measured QY of 4 in Zeonex was observed. No phosphorescent emission was detected.
Subject(s)
Chrysenes/chemistry , Gold/chemistry , Luminescence , Organogold Compounds , Photochemical Processes , Organogold Compounds/chemical synthesis , Organogold Compounds/chemistryABSTRACT
Polycyclic aromatic hydrocarbons (PAHs) have been a major concern because of their carcinogenicity, mutagenicity, teratogenicity and wide distribution in the environment. Over 90% of PAHs in the environment exist on soil surface/sediment. Benzo[a]pyrene (BaP) is one of the predominant PAHs in soil. Thus, it is critically important to understand the patterns of BaP accumulation and transformation peculiarities in soil for the risk assessment. The studies were conducted in model experiment with Haplic Chernozem spiked with various doses of BaP (20, 200, 400 and 800 µg kg-1) equivalent to 1, 10, 20 and 40 levels of maximum permissible concentrations. The unique properties of Haplic Chernozem were studied allow to accumulate and transform BaP as well as barley plants ability to absorb of some BaP concentration. Extraction of BaP from the soil was carried out by the saponification method. The qualitative and quantitative determination of BaP and other polycyclic aromatic hydrocarbons (PAHs) was performed by high-performance liquid chromatography with fluorescence detection (Agilent 1260 Germany, 2014). BaP accumulation in soil depended on the applied BaP concentrations in Haplic Chernozem. Studying the features of PAHs transformation in the soil of a model experiment 1 year after the compound application showed the BaP content in the soil decreased up to 11-40%. Two years after the BaP application the content in the soil decreased up to 15-44% from the initial BaP content in the soil. The percentage of BaP concentration reduction in Haplic Chernozem increased with an increase in the dose of the applied xenobiotic. An increase in the dose of the applied pollutant to the soil of the model experiment contributed to an increase in all PAHs, which indicated a rapid BaP transformation in Haplic Chernozem. The PAHs content in the soils of model experiment in the first year of the research formed the following descending series: pyrene > chrysene > fluoranthene > phenanthrene. In the second year of research the phenanthrene content became higher than the fluoranthene content. The content of these compounds exceeded 20% of the total PAHs content in the soil samples in the first and second years of the model experiment. The features of PAHs accumulation and transformation in soils under artificial pollution showed the degradation of large-nuclear PAHs, starting from 5-ring polyarenes, and their structural reorganization into the less-nuclear polyarenes, such as 4-, 3-, and 2-ring PAHs. During the 2 years of the model experiment the BaP concentration in the soil decreased up to 15-44% from the initial BaP content in the soil.
Subject(s)
Benzo(a)pyrene/metabolism , Soil Pollutants/metabolism , Benzo(a)pyrene/chemistry , Biodegradation, Environmental , Chrysenes/chemistry , Chrysenes/metabolism , Fluorenes/chemistry , Fluorenes/metabolism , Hordeum/metabolism , Phenanthrenes/chemistry , Phenanthrenes/metabolism , Polycyclic Aromatic Hydrocarbons/chemistry , Polycyclic Aromatic Hydrocarbons/metabolism , Pyrenes/chemistry , Pyrenes/metabolism , Russia , Soil/chemistry , Soil Pollutants/chemistryABSTRACT
The formation of polycyclic aromatic hydrocarbons (PAHs) is a strong global concern due to their harmful effects. To help the reduction of their emissions, a crucial understanding of their formation and a deep exploration of their growth mechanism is required. In the present work, the formation of benzo(a)pyrene was investigated computationally employing chrysene and benz(a)anthracene as starting materials. It was assumed a type of methyl addition/cyclization (MAC) was the valid growth mechanism in this case. Consequently, the reactions implied addition reactions, ring closures, hydrogen abstractions and intramolecular hydrogen shifts. These steps of the mechanism were computed to explore benzo(a)pyene formation. The corresponding energies of the chemical species were determined via hybrid density funcional theory (DFT), B3LYP/6-31+G(d,p) and M06-2X/6-311++G(d,p). Results showed that the two reaction routes had very similar trends energetically, the difference between the energy levels of the corresponding molecules was just 6.13 kJ/mol on average. The most stable structure was obtained in the benzo(a)anthracene pathway.
Subject(s)
Benz(a)Anthracenes/chemistry , Benzo(a)pyrene/chemistry , Carcinogens/chemistry , Polycyclic Aromatic Hydrocarbons/chemistry , Benz(a)Anthracenes/toxicity , Benzo(a)pyrene/toxicity , Carcinogens/toxicity , Chrysenes/chemistry , Humans , Hydrogen/chemistry , Molecular Structure , Polycyclic Aromatic Hydrocarbons/toxicityABSTRACT
Ebola virus (EBOV) causes a deadly hemorrhagic fever in humans and non-human primates. There is currently no FDA-approved vaccine or medication to counter this disease. Here, we report on the design, synthesis and anti-viral activities of two classes of compounds which show high potency against EBOV in both in vitro cell culture assays and in vivo mouse models Ebola viral disease. These compounds incorporate the structural features of cationic amphiphilic drugs (CAD), i.e they possess both a hydrophobic domain and a hydrophilic domain consisting of an ionizable amine functional group. These structural features enable easily diffusion into cells but once inside an acidic compartment their amine groups became protonated, ionized and remain trapped inside the acidic compartments such as late endosomes and lysosomes. These compounds, by virtue of their lysomotrophic functions, blocked EBOV entry. However, unlike other drugs containing a CAD moiety including chloroquine and amodiaquine, compounds reported in this study display faster kinetics of accumulation in the lysosomes, robust expansion of late endosome/lysosomes, relatively more potent suppression of lysosome fusion with other vesicular compartments and inhibition of cathepsins activities, all of which play a vital role in anti-EBOV activity. Furthermore, the diazachrysene 2 (ZSML08) that showed most potent activity against EBOV in in vitro cell culture assays also showed significant survival benefit with 100% protection in mouse models of Ebola virus disease, at a low dose of 10â¯mg/kg/day. Lastly, toxicity studies in vivo using zebrafish models suggest no developmental defects or toxicity associated with these compounds. Overall, these studies describe two new pharmacophores that by virtue of being potent lysosomotrophs, display potent anti-EBOV activities both in vitro and in vivo animal models of EBOV disease.
Subject(s)
Antiviral Agents/chemistry , Chrysenes/chemistry , Ebolavirus/drug effects , Hemorrhagic Fever, Ebola/drug therapy , Animals , Antiviral Agents/pharmacology , Antiviral Agents/toxicity , Chrysenes/pharmacology , Chrysenes/toxicity , Lysosomes/metabolism , Mice , Surface-Active Agents , Virus Internalization/drug effects , ZebrafishABSTRACT
GSK3532795, formerly known as BMS-955176 (1), is a potent, orally active, second-generation HIV-1 maturation inhibitor (MI) that advanced through phase IIb clinical trials. The careful design, selection, and evaluation of substituents appended to the C-3 and C-17 positions of the natural product betulinic acid (3) was critical in attaining a molecule with the desired virological and pharmacokinetic profile. Herein, we highlight the key insights made in the discovery program and detail the evolution of the structure-activity relationships (SARs) that led to the design of the specific C-17 amine moiety in 1. These modifications ultimately enabled the discovery of 1 as a second-generation MI that combines broad coverage of polymorphic viruses (EC50 <15 nM toward a panel of common polymorphisms representative of 96.5% HIV-1 subtype B virus) with a favorable pharmacokinetic profile in preclinical species.
Subject(s)
Anti-HIV Agents/chemistry , Anti-HIV Agents/pharmacology , Chrysenes/chemistry , Morpholines/chemistry , Structure-Activity Relationship , Triterpenes/chemistry , ATP Binding Cassette Transporter, Subfamily B, Member 1/genetics , Administration, Oral , Animals , Anti-HIV Agents/pharmacokinetics , Benzoic Acid/chemistry , Biological Availability , Chemistry Techniques, Synthetic , Chrysenes/pharmacology , Dogs , Drug Design , Drug Stability , HIV-1/drug effects , HIV-1/genetics , Humans , Macaca fascicularis , Male , Mice, Inbred Strains , Mice, Knockout , Microsomes, Liver/drug effects , Morpholines/pharmacology , Polymorphism, Genetic , Rats, Sprague-Dawley , Triterpenes/pharmacologyABSTRACT
Development of hybridization-based probes that enable recognition of specific mixed-sequence double-stranded DNA (dsDNA) regions is of considerable interest due to their potential applications in molecular biology, biotechnology, and medicine. We have recently demonstrated that nucleic acid duplexes with +1 interstrand zipper arrangements of intercalator-functionalized nucleotides such as 2'-O-(pyren-1-yl)methyl RNA monomers are inherently activated for recognition of mixed-sequence dsDNA targets, including chromosomal DNA. In the present work, we follow up on our previous structure-activity relationship studies and explore if the dsDNA-recognition efficiency of these so-called Invader probes can be improved by using larger intercalators than pyrene. Oligodeoxyribonucleotides modified with 2'-O-(triphenylen-2-yl)methyl-uridine monomer X and 2'-O-(coronen-1-yl)methyl-uridine monomer Z form extraordinarily stabilized duplexes with complementary DNA (ΔTm's per modification of up to 13 °C and 20 °C, respectively). Invader probes based on X- and Z-monomers are shown to recognize model dsDNA targets with exceptional binding specificity, but are less efficient than reference probes modified with 2'-O-(pyren-1-yl)methyl-uridine monomer Y. The insight from this study will inform further optimization of Invader probes.
Subject(s)
Chrysenes/chemistry , DNA/chemistry , Polycyclic Compounds/chemistry , RNA/chemistry , Base Sequence , DNA/genetics , Inverted Repeat Sequences , Nucleic Acid Denaturation , Structure-Activity Relationship , Temperature , Uridine/chemistryABSTRACT
Polyvinyl pyrrolidone (PVP) crowned chrysene nanoparticles (CHYNPs) were prepared by using a reprecipitation method. Dynamic light scattering (DLS) and scanning electron microscope (SEM) studies indicate that the monodispersed spherical nanoparticles bear a negative charge on their surfaces. The bathochromic spectral shift in the UV-visible and fluorescence spectrum of CHYNPs from chrysene (CHY) in acetone solution supports the J- type aggregation of nanoparticles. The aggregation-induced enhanced emission of CHYNPs at 486 and 522 nm decreases by increasing the concentration of the Ca2+ ion solution. It can display an ON-OFF type fluorescence response with high selectivity towards Ca2+ ions aqueous medium. Furthermore, the in situ generated PVP-CHYNPs-Ca2+ ensemble could recover the quenched fluorescence upon the addition of fluoride anions resulting in an OFF-ON type sensor. The present method has a correlation coefficient R2 = 0.988 with a detection limit of 1.22 µg/mL for Ca2+ in the aqueous medium. The fluorescence changes of PVP crowned CHYNPs upon the addition of Ca2+ and F- can be utilized as an INHIBIT logic gate at the molecular level, using Ca2+ and F- chemical inputs and the fluorescence intensity signal as output.
Subject(s)
Calcium/analysis , Chrysenes/chemistry , Iron/analysis , Luminescent Agents/chemistry , Nanoparticles/chemistry , Anions/chemistry , Dynamic Light Scattering , Fluorides/chemistry , Hydrogen-Ion Concentration , Microscopy, Electron, Scanning , Particle Size , Povidone/chemistry , Spectrometry, Fluorescence , Spectrophotometry, Ultraviolet , WaterABSTRACT
The mechanisms of naphthacene and triphenylene discrimination using commercially available cellulose tris(4-methylbenzoate) (CMB) and cellulose tribenzoate (CB) chiral stationary phases were investigated using molecular mechanics calculations. Naphthacene and triphenylene could be separated by liquid chromatography on CMB and CB, with triphenylene being eluted earlier than naphthacene on both phases. However, the corresponding separation factor is much larger for CMB than for CB. The docking of these polycyclic aromatic hydrocarbons to the above polymers suggested that the most important sites of CMB and CB for interacting with these hydrocarbons are located at equivalent positions, featuring a space surrounded by main chain glucose units and benzoyl side chains. The difference of hydrocarbon stabilization energies with CMB and CB agreed well with the observed chromatographic separation factors.
Subject(s)
Benzoates/chemistry , Cellulose/analogs & derivatives , Chrysenes/isolation & purification , Naphthacenes/isolation & purification , Binding Sites , Carbohydrate Conformation , Cellulose/chemistry , Chromatography, High Pressure Liquid , Chrysenes/chemistry , Molecular Docking Simulation , Naphthacenes/chemistry , ThermodynamicsABSTRACT
This paper describes the synthesis of a trinuclear Cu(II) complex (4) containing a central 1,4,5,8,9,12-hexaazatriphenylene-hexacarboxylate (hat) core (3). Low, micromolar concentrations of the negatively charged parent ligand 3 and the neutral trinuclear complex 4 were found to photocleave negatively charged pUC19 plasmid DNA with high efficiency at neutral pH (350nm, 50min, 22°C). The interactions of complex 4 with double-helical DNA were studied in detail. Scavenger and colorimetric assays pointed to the formation of Cu(I), superoxide anion radicals, hydrogen peroxide, and hydroxyl radicals during photocleavage reactions. UV-visible absorption, circular dichroism, DNA thermal denaturation, and fluorescence data suggested that the Cu(II) complex contacts double-stranded DNA in an external fashion. The persistent association of ligand 3 and complex 4 with Na(I) and/or other cations in aqueous solution might facilitate electrostatic DNA interactions.
Subject(s)
Aza Compounds/chemistry , Aza Compounds/pharmacology , Chrysenes/chemistry , Chrysenes/pharmacology , Copper/chemistry , Copper/pharmacology , DNA/drug effects , DNA/metabolism , Photochemical Processes , Circular Dichroism , Colorimetry , Hydrogen Peroxide/chemistry , Molecular Structure , Superoxides/chemistryABSTRACT
We investigated the photophysical properties of difluoroboronated ß-diketones (BF2DK) with chrysene and pyrene skeletons (ChB and PyB, respectively) in solution and in the solid state. Acetylchrysenes, as the key precursors to ChBs, were photochemically prepared from the corresponding (acetylphenyl)naphthylethenes by means of a modified photocyclization method. The absorption and emission spectra of the BF2DKs were obtained in chloroform and acetonitrile, and the quantum yields and lifetimes of the fluorescence were determined. Excimeric fluorescence from PyB was absent even in highly concentrated solution. Based on the Lippert-Mataga analysis of the absorption and fluorescence features, the photophysical properties of the ChBs were discussed in comparison with those of PyB. The fluorescence states of the studied BF2DKs are shown to be of a charge-transfer character. The fluorescence quantum yields decrease with increasing the solvent polarity due to the enhanced internal conversion process. The fluorescence quantum yields in the solid state of the studied BF2DKs were determined, and it was found that PyB is fluorescent, whereas the fluorescence quantum yields of the ChBs depend on the substituted position of the chrysene moiety.
Subject(s)
Chrysenes/chemistry , Pyrenes/chemistry , Acetonitriles/chemistry , Chrysenes/chemical synthesis , Cyclization , Pyrenes/chemical synthesis , Quantum Theory , Solvents/chemistry , Spectrometry, Fluorescence , X-Ray DiffractionABSTRACT
Exposure to polycyclic aromatic hydrocarbons (PAHs) is the major human health hazard associated with the Deepwater Horizon oil spill. C2-Chrysenes are representative PAHs present in crude oil and could contaminate the food chain. We describe the metabolism of a C2-chrysene regioisomer, 6-ethylchrysene (6-EC), in human HepG2 cells. The structures of the metabolites were identified by HPLC-UV-fluorescence detection and LC-MS/MS. 6-EC-tetraol isomers were identified as signature metabolites of the diol-epoxide pathway. O-Monomethyl-O-monosulfonated-6-EC-catechol, its monohydroxy products, and N-acetyl-l-cysteine(NAC)-6-EC-ortho-quinone were discovered as signature metabolites of the ortho-quinone pathway. Potential dual metabolic activation of 6-EC involving the formation of bis-electrophiles, i.e., a mono-diol-epoxide and a mono-ortho-quinone within the same structure, bis-diol-epoxides, and bis-ortho-quinones was observed as well. The identification of 6-EC-tetraol, O-monomethyl-O-monosulfonated-6-EC-catechol, its monohydroxy products, and NAC-6-EC-ortho-quinone supports potential metabolic activation of 6-EC by P450 and AKR enzymes followed by metabolic detoxification of the ortho-quinone through interception of its redox cycling capability by catechol-O-methyltransferase and sulfotransferase enzymes. The tetraols and catechol conjugates could be used as biomarkers of human exposure to 6-EC resulting from oil spills.
Subject(s)
Alkaline Phosphatase/metabolism , Catechol O-Methyltransferase/metabolism , Chrysenes/chemistry , Chrysenes/metabolism , Cytochrome P-450 Enzyme System/metabolism , Petroleum Pollution/analysis , Sulfotransferases/metabolism , Chrysenes/analysis , Hep G2 Cells , Humans , Molecular Structure , Tumor Cells, CulturedABSTRACT
A series of triphenylenes with oligoethoxy chains of various length, TP6EOnM with n = 2, 3, 4, has been synthesised and purified by HPLC. The self-association of these disc-shaped molecules in dilute aqueous solutions (â¼10(-7) to â¼4 × 10(-4) M) has been studied by UV-visible absorption spectroscopy. The free energy of association decreases as the length of the chains increases. As a result, for a given concentration, the average size of aggregate diminishes as the chain length increases. While the absorption properties of the monomer are identical for the three molecules, the extinction coefficients of solutions of the three triphenylenes at a given concentration are significantly different and are directly linked to the average size of the aggregates. The change of epsilon values upon aggregation could explain the trend generally observed with dyes for solar cells substituted with chains of increasing length showing increasing extinction coefficient values.
Subject(s)
Chrysenes/chemistry , Coloring Agents/chemistry , Water/chemistry , Absorption, Radiation , Solutions , Spectrophotometry, Ultraviolet , Structure-Activity Relationship , ThermodynamicsABSTRACT
Degradation of chrysene, a four ringed highly carcinogenic polycyclic aromatic hydrocarbon (PAH) has been demonstrated by bacterial mixed culture Biorem-CGBD comprising Achromobacter xylosoxidans, Pseudomonas sp. and Sphingomonas sp., isolated from crude oil polluted saline sites at Bhavnagar coast, Gujarat, India. A full factorial Central Composite Design (CCD) using Response Surface Methodology (RSM) was applied to construct response surfaces, predicting 41.93% of maximum chrysene degradation with an experimental validation of 66.45% chrysene degradation on 15th day, using a combination of 0.175, 0.175 and 0.385 mL of OD600 = 1 inoculum of A. xylosoxidans, Pseudomonas sp. and Sphingomonas sp., respectively and a regression coefficient (R2) of 0.9485 indicating reproducibility of the experiment. It was observed that chrysene degradation can be successfully enhanced using RSM, making mixed culture Biorem-CGBD a potential bioremediation target for PAH contaminated saline sites.
Subject(s)
Biodegradation, Environmental , Chrysenes/chemistry , Polycyclic Aromatic Hydrocarbons/chemistry , Achromobacter denitrificans/chemistry , Achromobacter denitrificans/metabolism , Carcinogens/chemistry , Carcinogens/metabolism , Chrysenes/toxicity , Humans , Polycyclic Aromatic Hydrocarbons/toxicity , Pseudomonas/chemistry , Pseudomonas/metabolism , Sphingomonas/chemistry , Sphingomonas/metabolismABSTRACT
Although concentrations of alkylated polycyclic aromatic hydrocarbons (alkyl-PAHs) in oil-contaminated sediments are higher than those of unsubstituted PAHs, only little attention has been given to metabolism and ecotoxicity of alkyl-PAHs. In this study we demonstrated that metabolism of alkyl-PAHs primarily forms polycyclic aromatic acids (PAAs). We generalize this to other alkyl-PAHs, based on literature and the present study of the metabolism of 1-methylphenanthrene, 3,6-dimethylphenanthrene, and 1-, 2-, 3-, and 6-methylchrysene related to their unsubstituted parent PAHs. Also, we observed that body burdens and production of PAAs was related to the position of the methyl group, showing the same isomer specific preferences as for microbial degradation of alkyl-PAHs. We detected a high production of PAAs, and larger metabolism of alkyl-PAHs than their unsubstituted parent PAHs. We therefore propose that carboxylic acid metabolites of alkyl-PAHs have the potential of constituting a new class of contaminants in marine waters that needs attention in relation to ecological risk assessments.
Subject(s)
Invertebrates/metabolism , Metabolome , Polycyclic Aromatic Hydrocarbons/metabolism , Animals , Chrysenes/chemistry , Fluorescence , Phenanthrenes/chemistry , Water/chemistryABSTRACT
Alkylated polycyclic aromatic hydrocarbons (alkyl-PAHs) are a class of compounds found at significant concentrations in crude oils, and likely the main constituents responsible for the chronic toxicity of oil to fish. Alkyl substituents at different locations on the aromatic rings change the size and shape of PAH molecules, which results in different interactions with tissue receptors and different severities of toxicity. The present study is the first to report the toxicity of several alkylated derivatives of chrysene and benz[a]anthracene to the embryos of Japanese medaka (Oryzias latipes) using the partition controlled delivery (PCD) method of exposure. The PCD method maintained the desired exposure concentrations by equilibrium partitioning of hydrophobic test compounds from polydimethylsiloxane (PDMS) films. Test concentrations declined by only 13% over a period of 17 days. Based on the prevalence of signs of blue sac disease (BSD), as expressed by median effective concentrations (EC50s), benz[a]anthracene (B[a]A) was more toxic than chrysene. Alkylation generally increased toxicity, except at position 2 of B[a]A. Alkyl-PAHs substituted in the middle region had a lower EC50 than those substituted at the distal region. Except for B[a]A and 7-methylbenz[a]anthracene (7-MB), estimated EC50 values were higher than their solubility limits, which resulted in limited toxicity within the range of test concentrations. The regression between log EC50s and logKow values provided a rough estimation of structure-activity relationships for alkyl-PAHs, but Kow alone did not provide a complete explanation of the chronic toxicity of alkyl PAHs.
Subject(s)
Anthracenes/chemistry , Anthracenes/toxicity , Chrysenes/chemistry , Chrysenes/toxicity , Oryzias/physiology , Alkylation , Animals , Embryo, Nonmammalian/drug effects , Petroleum , Polycyclic Aromatic Hydrocarbons/toxicity , Quantitative Structure-Activity Relationship , Structure-Activity Relationship , Water Pollutants, Chemical/chemistry , Water Pollutants, Chemical/toxicityABSTRACT
In this contribution, we finely tuned the singlet-triplet energy gap (ΔEST) of AIE-active materials to modulate their fluorescence, phosphorescence and delay fluorescence via rational molecular design and investigated the possible ways to harvest their triplet energy in OLEDs. Noteworthily, two molecules o-TPA-3TPE-o-PhCN and o-TPA-3TPE-p-PhCN with larger ΔEST values (0.59 eV and 0.45 eV, respectively) emitted efficient long-lived low temperature phosphorescence in their glassy solutions and exhibited efficient crystallization-induced room temperature phosphorescence (RTP). Meanwhile, it was the first time to observe a novel crystallization-induced delay fluorescence phenomenon in another AIE-active molecule p-TPA-3TPE-p-PhCN owing to its very small ΔEST value (0.21 eV). It was also found that molecules with various ΔEST values showed significantly different temperature sensitivity. Non-doped electroluminescent (EL) devices using these molecules as light-emitting layers were fabricated, exhibiting external quantum efficiencies (EQE) higher than theoretical values of purely singlet emitter type devices. Particularly, p-TPA-3TPE-p-PhCN showed outstanding device performances with high luminance and efficiencies up to 36,900 cd m(-2), 11.2 lm W(-1), 12.8 cd A(-1) and 4.37%, respectively, considering that its solid-state quantum yield was only 42%. All the above observations suggested that tuning the ΔEST values of AIE materials is a powerful methodology to generate many more interesting and meaningful optoelectronic properties.