变色栓菌中的漆酶通过功能化纳米颗粒SBA-15进行固定，其平均直径小于10纳米。研究了在两种介质2,2'-偶氮双-(3-乙基苯并噻唑啉-6-磺酸)二铵盐（ABTS）和1-羟基苯并三唑（HBT）存在下，漆酶介导的蒽（ANT）氧化反应。添加1 mM HBT比添加ABTS更有效地增强了ANT的氧化。经过48小时氧化，HBT组显著氧化ANT，残留量为58%，而ABTS组为88%。高效液相色谱（HPLC）和气相色谱/质谱（GC/MS）分析表明，ANT氧化的主要产物是蒽醌（ANQ）。使用两种人类细胞系对ANT和ANQ的细胞毒性和遗传毒性进行了评估。以5和10微摩尔处理的ANT和ANQ对HaCaT细胞和A3淋巴细胞表现出显著的细胞毒性，没有观察到显著的遗传毒性。结果表明，ANQ的毒性低于ANT。
The laccase of Trametes versicolor was immobilized on the functionalized nanoparticles SBA-15 with the average diameter less than 10 nm. Laccase mediated oxidations of anthracene (ANT) were investigated in the presence of two mediators, 2,2'-azino-bis-(3-ethylbenzothiazoline-6-sulphonic acid) diammonium salt (ABTS) and 1-hydroxybenzotriazole (HBT). Oxidation of ANT was more efficiently enhanced by adding 1 mM of HBT than that by adding ABTS. After 48 hr oxidation HBT group significantly oxidized ANT with residue 58% relative to 88% in the ABTS group. HPLC and GC/MS analyses indicated the main product of ANT oxidation was anthraquinone (ANQ). The fluorescein diacetate (FDA) uptake of two human cell lines was used to assess the cytotoxicity and genotoxicity of ANT and ANQ. Treatments with ANT and ANQ at 5 and 10 uM exhibited significant cytotoxicity to the HaCaT cells and the A3 lymphocytes and no significant genotoxicity was observed. The results illustrated that ANQ is less toxic than ANT as well.
Hemoglobin is a member of the hemoprotein superfamily whose main role is to transport O(2) in vertebrate organisms. It has two known promiscuous enzymatic activities, peroxidase and oxygenase. Here we show ... that bovine hemoglobin also presents a catalase-like activity characterized by a V(max )of 344 uM/min, a K(M)of 24 mM and a k(cat) equal to 115/min. For high anthracene and hemoglobin concentrations and low hydrogen peroxide concentrations, this activity inhibits the expected oxidation of anthracene, which occurs through a peroxidase-like mechanism. Anthracene belongs to the polycyclic aromatic hydrocarbon (PAH) family whose members are carcinogenic and persistent pollutants found in industrial waste waters. Our results show that anthracene oxidation by hemoglobin and hydrogen peroxide follows a typical bi-bi ping-pong mechanism with a V(max) equal to 0.250 uM/min, K(M(H2O2) )of 80 uM, K(M(ANT)) of 1.1 uM and k(cat) of 0.17/min. The oxidation of anthracene is shown to be pseudo-catalytic because an excess of hemoglobin and hydrogen peroxide is required to make PAH completely disappear. Thus, bovine hemoglobin presents, in different degrees, all the catalytic activities of the hemoprotein group ... .
When administered orally to animals ... (70-80% of dose) is excreted unchanged in feces, but metabolites present in rat urine include n-acetyl-s-(1,2-dihydro-2-hydroxy-1-anthryl)-cysteine and conjugates of trans-1,2-dihydroanthracene-1,2-diol, and 1,2-dihydroxyanthracene. The cysteine conjugate is decomposed by mineral acids to yield 1-anthrylmercapturic acid, 1 and 2-anthrols and anthracene. Rats ... metabolize anthracene into trans-9,10-dihydroanthracene-9,10-diol, which gives rise to anthrone and several hydroxylated metabolites.
In vitro metabolism of anthracene with rat liver microsomes predominantly forms trans-1,2-dihydroxy-1,2-dihydroanthracene with little evidence of metabolism at the 9,10-position.
PAH metabolism occurs in all tissues, usually by cytochrome P-450 and its associated enzymes. PAHs are metabolized into reactive intermediates, which include epoxide intermediates, dihydrodiols, phenols, quinones, and their various combinations. The phenols, quinones, and dihydrodiols can all be conjugated to glucuronides and sulfate esters; the quinones also form glutathione conjugates. (L10)
IDENTIFICATION AND USE: Anthracene (ANT) is a solid. It is used as an intermediate for dyes, alizarin, phenanthrene, carbazole, anthraquinone, calico printing, a component of smoke screens, scintillation counting crystals, and in organic semiconductor research. HUMAN EXPOSURE AND TOXICITY: Melanosis coli is associated with an increased risk of colorectal tumors but is not agreed to be a precancerous lesion. The condition has been associated with the ingestion of ANT laxatives and is believed to be caused by increased epithelial apoptosis. In a longitudinal analysis from 1946 to 2002, a total of 618 employees with exposure to soot, raw paraffin, tar, anthracene, pitch or similar substances were examined. Squamous cell carcinomas, basal cell carcinomas, keratoacanthomas and melanomas were diagnosed. ANT failed in a large number of studies to induce unscheduled DNA synthesis in human HeLa cells with metabolic activation, while it gave a marginally positive, nondose-related response in primary human skin epithelial cells. It yielded negative results in tests for forward mutation in human lymphoblastoid cells (36 ug/mL). UV radiation (295 nm) induced covalent binding of ANT to DNA which increased with time and was not affected by oxygen. Irradiation of human serum albumin in the presence of ANT induced covalent binding of the hydrocarbon to the protein accompanied by cross-linking of the protein. Protein cross-linking decreased under anaerobic conditions. ANIMAL STUDIES: Very slight erythema and/or edema was observed in five of six rabbits after skin application. Tests for complete carcinogenicity and initiating activity in mouse skin-painting assays have not shown positive results. ANT has been tested in a number of studies for skin carcinogenicity in combination with UV or visible radiation. The group of mice receiving the combined ANT and UV treatment showed "broadness of the epidermis", but no skin papillomas or carcinomas were observed in either group. ANT has been tested for the induction of genotoxicity (DNA damage and mutations) in a large number of bacterial systems, including Escherichia coli, Salmonella typhimurium and Bacillus subtilis, with and without metabolic activation, giving negative results in the great majority of cases. ANT has been tested for the induction of sister chromatid exchanges in Chinese hamster ovary cells with metabolic activation, in a rat liver epithelial cell line and in a combined in vitro/in vivo test using Chinese hamster V79 cells implanted into mice. All studies reported negative results except for one which was marginally positive. ECOTOXICITY STUDIES: ANT exposure generated compound-dependent oxidative stress in the tissues of V. decussata. Acute mortality of bluegill sunfish, Lepomis macrochirus, dosed with ANT at 12.7 ug/L and exposed to natural sunlight conditions was observed during a study of ANT fate in outdoor channel microcosms. No mortality was observed under control conditions (natural sunlight and no ANT). The results obtained in short-term experiments with algae indicate that ANT acts as a photosensitizer causing an oxidative damage of cells.
The ability of PAH's to bind to blood proteins such as albumin allows them to be transported throughout the body. Many PAH's induce the expression of cytochrome P450 enzymes, especially CYP1A1, CYP1A2, and CYP1B1, by binding to the aryl hydrocarbon receptor or glycine N-methyltransferase protein. These enzymes metabolize PAH's into their toxic intermediates. The reactive metabolites of PAHs (epoxide intermediates, dihydrodiols, phenols, quinones, and their various combinations) covalently bind to DNA and other cellular macromolecules, initiating mutagenesis and carcinogenesis. (L10, L23, A27, A32)
来源:Toxin and Toxin Target Database (T3DB)
毒理性
致癌性证据
总评：第3组：该物质对人类致癌性无法分类。
OVERALL EVALUATION: Group 3: The agent is not classifiable as to its carcinogenicity to humans.
CLASSIFICATION: D; not classifiable as to human carcinogenicity. BASIS FOR CLASSIFICATION: Based on no human data and inadequate data from animal bioassays. HUMAN CARCINOGENICITY DATA: None. ANIMAL CARCINOGENICITY DATA: Inadequate. /Based on former classification system/
来源:Hazardous Substances Data Bank (HSDB)
毒理性
致癌物分类
国际癌症研究机构致癌物：蒽
IARC Carcinogenic Agent:Anthracene
来源:International Agency for Research on Cancer (IARC)
Polycyclic aromatic hydrocarbons were detected in human fat and liver and their average concentrations were 1100 and 380 ppt, respectively. Anthracene was found at high levels in the liver and fat.
(14)Carbon -labeled anthracene was administered to young Coho Salmon in food and by ip injection. The accumulated (14)carbon in key organs (eg, liver and brain) increased over various time periods. After ip injection, the highest percent of metabolites occurred in gallbladder; however, significant amounts were also found in the liver, brain, flesh, and carcass. It appears that aromatic metabolites are broadly distributed throughout fish exposed to polynuclear aromatic hydrocarbons.
Five normal adult volunteers without cutaneous disease applied to their skin a 2% solution of crude coal tar in petrolatum, containing 190 mg/L anthracene. In total, 85 g of the solution were applied for 8-hour periods on two consecutive days. Organic extracts of blood collected after completion of the second application and subjected to gas chromatography and mass spectrometry yielded evidence of anthracene adsorption in four of the five volunteers, with blood concentrations ranging 0.08-0.47 ug/L.
... Conscious rats with bile duct and duodenal catheters were given isotopically labelled anthracene (1 mg in 0.2 mL in corn oil, corresponding to 3.7 mg/kg), and the recovery of radioactivity in bile and urine was measured. One group of animals received via the duodenal catheter only anthracene solution, whereas a second group received the anthracene solution mixed with 0.5 mg bile, followed by 8 further doses of 0.5 mL bile at hourly intervals to simulate normal bile flow. Over the next 24 hours, samples of bile and urine were collected and the amount of radiolabel recovered was measured as an index of the efficiency of absorption. Irrespective of the presence or absence of bile, about two thirds of the radioactivity absorbed was found in the bile and one third in the urine. Cumulative recovery in the presence of bile was 75.55% of the administered dose, while in the absence of bile it was somewhat lower (53.65%), a finding attributed to the relatively low water solubility of anthracene and suggesting that bile-mediated micellar solubilisation facilitates the uptake process. While this study indicates that, over a period of 24 hours, at least 75% of orally administered anthracene is initially absorbed from the intestinal tract of rats with normal bile flow; in the absence of information on the amount of unmetabolized anthracene present in biliary secretions the net systemic absorption of anthracene via the intestine cannot be estimated.
Biphasic copper-catalyzed C–H bond activation of arylalkanes to ketones with tert-butyl hydroperoxide in water at room temperature
作者：Md. Munkir Hossain、Shin-Guang Shyu
DOI：10.1016/j.tet.2016.05.066
日期：2016.7
A facile C–H bond activation of arylalkanes to their corresponding ketones catalyzed by copper salts using tert-butyl hydroperoxide as an oxidant in water at room temperature is described. Easy product separation, simple reaction procedures (without using base or phase transfer catalysis), and catalyst recycling make the catalytic system attractive. It is also active beyond activated benzylic methylene
Effect of Ligand Fields on the Reactivity of O
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‐Activating Iron(II)‐Benzilate Complexes of Neutral N5 Donor Ligands
作者：Shrabanti Bhattacharya、Reena Singh、Tapan Kanti Paine
DOI：10.1002/asia.202000142
日期：2020.4.17
Three new iron(II)-benzilate complexes [(N4Py)FeII (benzilate)]ClO4 (1), [(N4PyMe2 )FeII (benzilate)]ClO4 (2) and [(N4PyMe4 )FeII (benzilate)]ClO4 (3) of neutral pentadentate nitrogen donor ligands have been isolated and characterized to study their dioxygen reactivity. Single-crystal X-ray structures reveal a mononuclear six-coordinate iron(II) center in each case, where benzilate binds to the iron
direct CH arylation of (hetero)arenes. Starting from an aniline, the corresponding arenediazonium ion is generated in situ and immediately reduced by vitamin C to an aryl radical that undergoes a homolytic aromatic substitution with a (hetero)arene. Notably, neither heating nor irradiation is required. This procedure is mild, operationally simple, and constitutes a greener approach to arylation.
A new synthesis of n-acyl aromatic α-amino acids—amidoalkylation of aromatic and heterocyclic compounds with glyoxylic acid derivatives
作者：D. Ben-Ishai、I. Sataty、Z. Bernstein
DOI：10.1016/0040-4020(76)85215-5
日期：1976.1
The synthesis of N-acyl derivatives of aromatic α-amino acids 5 by the amidoalkylations of aromatic and heterocyclic compounds with glyoxylic acid amide adducts is described.
