Free Aromatic Amines Research Articles

Novel insecticide waterborne coating based on isoxazole benzene sulfonamide derivatives as insecticide agents

PurposePaper aims to Preparation and evaluation of isoxazole benzene sulfonamide derivatives and incorporated it with waterborne household paints to develop coating compositions as an insecticidal coating against Musca domestica adults.Design/methodology/approachThe synthesized compounds were prepared and confirmed by different analyzes, fourier transform infra-red (FTIR), mass, proton nuclear magnetic resonance (1HNMR) and Carbon 13 nuclear magnetic resonance (13CNMR) spectra. The prepared compound has been blended with waterborne household paint formulation, the physical and mechanical properties of the paint formulation has been studied. The efficiency of the isoxazole benzene sulfonamide derivatives when incorporated with waterborne paint against Culex quinquefasciatus and Mosquito house fly adults, also have been examined.FindingsThe obtained results of the paint formulations confirmed their best performance and providing good scrub resistance. Also, the finding promising results of the insecticide test of the paint formulation may be because of the biological activity of these compounds and containing sulfonamide, cyanide and free aromatic amine groups comparing with the standard recommended organophosphorus insecticide. The order activity increase with increasing the dose concentration of the isoxazole derivatives and the activity of chemical compounds itself is represented in terms of their medium lethal concentrations LC50 (LC90), which recorded 0.90(1.62), 0.89(1.61) and 0.86(1.56) g/ml for 5, 3 and 4 chemical compounds, respectively, after 72 h from treatment.Practical implicationsThese types of organic compounds are friendly environmentally and can be used as a biocide with different types of paint formulations.Originality/valueInsecticide waterborne household paints based on isoxazole benzene sulfonamide derivatives as insecticide agents are novel.

Characterization of stress degradation products of nintedanib by UPLC, UHPLC-Q-TOF/MS/MS and NMR: Evidence of a degradation product with a structure alert for mutagenicity

Nintedanib is an anti-cancer drug used for the treatment of idiopathic pulmonary fibrosis and non-small cell lung cancer. The purpose of this study was to explore its degradation chemistry under various stress conditions recommended in ICH guidelines Q1A R(2). The drug was subjected to hydrolytic, photolytic, thermal and oxidative (H2O2, AIBN, FeCl3 and FeSO4) stress conditions. The degradation products formed in stressed solutions were successfully separated on an ACQUITY UPLC CSH C18 (2.1 × 100 mm, 1.7 μm) column, using a gradient UPLC-PDA method, developed with acetonitrile:methanol (90:10) and 0.1 % formic acid (pH 3.0) as the mobile phase. The drug proved to be labile to acidic, neutral and alkaline hydrolytic, and H2O2/AIBN oxidative conditions. It was stable to photolytic and thermal stress conditions, and even in oxidative reaction solutions containing FeCl3 or FeSO4. Additionally, the drug exhibited instability when its powder with added sodium bicarbonate was stored at 40 °C/75 % RH for 3 months. In total, nine degradation products (DPs 1–9) were formed. To characterize them, a comprehensive mass fragmentation pathway of the drug was first established using UHPLC-Q-TOF/MS/MS data. Similarly, the mass studies were then carried out on the stressed samples using the developed UPLC method. All the degradation products were primarily characterized through comparison of their mass fragmentation profiles with that of the drug. To confirm the structure in one case (DP 3), additional nuclear magnetic resonance (NMR) studies were carried out on the isolated product. Subsequently, mechanisms for their formation were laid down. A significant finding was the formation of a degradation product upon acid hydrolysis having a free aromatic amine moiety, which is considered as a structural alert for mutagenicity. Furthermore, the physicochemical and ADMET properties of the drug and its degradation products were predicted using ADMET predictor™ software.

Use of Acidic Hydrolysis and Diazo Coupling Reaction for Spectrophotometric Determination of Furosemide in Urine and Pharmaceutical Formulation.

Simple and rapid spectrophotometric determination of furosemide (FUR) has been investigated .The method is based on acid hydrolysis of FUR to free primary aromatic amine and diazotization followed by coupling with 3, 5 di methyl phenol (3, 5-DMPH) at basic medium. The absorbance was measured at 434 nm, the method was optimized for best condition, and beers’ law is obeyed over the range of 0.4-50 µg.mL-1 with molar absorptivity and sandal’s sensitivity 1.3899 x104 L moL-1 .cm-1 and 0.0238x104 µg.cm-2 respectively. Analysis of solution containing nineteen different concentrations of FUR gave a correlation coefficient of (0.9999) and limit of detection, limit of quantitation were 0.127, 0.464µg.mL-1 respectively. The reaction stoichiometry was evaluated by Job’s and mole ratio method was found to be 1:1(diazotized FUR: 3, 5-DMPH) .The method was applied in synthetic urine and pharmaceutical formulation. The recovery of FUR in spiked urine was satisfactory resulting in the values of (99±3.32) %, the results of the suggested method was compared with available official literature method.

NH2-Directed C-H Alkenylation of 2-Vinylanilines with Vinylbenziodoxolones.

The first directing-group-mediated C-H alkenylation with alkenyl-λ3-iodanes as electrophilic alkene-transfer reagents has been developed. The application of free aromatic amines as challenging but synthetically valuable directing groups in combination with an IrIII catalyst enabled the synthesis of highly desirable 1,3-dienes in excellent yields of up to 98% with high to perfect (Z,E) stereoselectivity. A broad substrate scope and further synthetic modifications are demonstrated.

Azo dye decolorization by ZVI under circum-neutral pH conditions and the characterization of ZVI corrosion products

Abstract This study examined the effects of initial solution pH (pHi), ZVI dosage, initial Trypan Blue (TB) concentration ([TB]0), and background electrolytes (NaCl and NaNO3) on the rate and extent of dye decolorization. TB azo dye ([TB]0 = 90 μM) was almost completely removed in 1320 min at pHi 4, while only 54% at pHi 10. The effects of Cl− and NO3− as a common major anion (10 mM) were contrasting on the efficiency of ZVI decolorization. The former accelerated the decolorization presumably due to impeding surface passivation of secondary Fe (oxyhydr)oxides by forming dissolved Fe–Cl complexes. On the contrary, the latter promoted the formation of secondary oxide layers resulting in the declining the ZVI reactivity. The XRD spectra of reacted ZVI particles suggested that lepidocrocite was initially formed as the ZVI corrosion products, which gradually transformed to magnetite. FT-IR spectroscopy revealed the decolorization processes as the destruction of N N bond in TB dye structure, followed by the formation of free aromatic amine groups ( NH2) after 1320 min of reaction with ZVI. The experimental results demonstrated that the novel ZVI treatment system could be a potential and promising alternative technique to remove TB dye by reductive decolorization treatment processes.

Variation in amine composition in plant species:How it integrates macroevolutionary and environmental signals

While plants show lineage-specific differences in metabolite composition, plant metabolites are also known to vary in response to the environment. The extent to which these different determinants of metabolite composition are mutually independent and recognizable is unknown. Moreover, the extent to which the metabolome can reconcile evolutionary constraint with the needs of the plant for rapid environmental response is unknown. We investigated these questions in plant species representing different phylogenetic lineages and growing in different subantarctic island environments. We studied their amines-metabolites involved in plant response to environmental conditions. Nine species were sampled under high salinity, water saturation, and altitude on the Kerguelen Islands. Their profiles of free aromatic, aliphatic, and acetyl-conjugated amines were determined by HPLC. We related amine composition to species and environment using generalized discriminant analyses. Amine composition differed significantly between species within the same environment, and the differences reflected phylogenetic positions. Moreover, across all species, amine metabolism differed between environments, and different lineages occupied different absolute positions in amine/environment space. Interestingly, all species had the same relative shifts in amine composition between environments. Our results indicate a similar response of amine composition to abiotic environments in distantly related angiosperms, suggesting environmental flexibility of species is maintained despite major differences in amine composition among lineages. These results aid understanding of how in nature the plant metabolome integrates ecology and evolution, thus providing primordial information on adaptive mechanisms of plant metabolism to climate change.

Fast and easy detection of aromatic amines on solid support

The use of p-nitrophenyl ester 1 has been shown to offer a reliable method for the detection of free aromatic amines. As little as 3.4 μmol g −1 of free aniline amino groups can be detected. The method has shown to be more sensitive for the detection of sterically hindered aromatic amines than the existing alternative based on reaction with chloranil.

An efficient chemo and regioselective oxidative nuclear bromination of activated aromatic compounds using lithium bromide and ceric ammonium nitrate

A mild, efficient and highly chemo- and regioselective method for the bromination of electron rich aromatic molecules has been developed by electrophilic substitution of Br +, which was generated in situ from LiBr using ceric ammonium nitrate as the oxidant. Free aromatic amines remained unaffected under the reaction conditions.

Determination of Free Aromatic Amines in Radiodiagnostic Preparation using Segmented Flow Analysis

ABSTRACT A flow-through method for the determination of free aromatic amines in radiodiagnostic preparation was developed. The concentration range of determination, sensitivity of measurement, limit of detection and determination, and repeatability of measurement were found. The method was tested for the analysis of the compound Iodipamide.

A Simple, General and Efficient Method for O and N-Retinoylation. Application to The Synthesis of 2-Retinoyl-Lecithin

The synthesis of the new l-stearoyl-2-retinoyl-glycero-3-phosphorylcholine by coupling of retinoic acid and lysolecithin with DCC-DMAP (1.2 eq.) is reported. This method is applied to O and N-retinoylation of uncharged organic substrates such as aliphatic alcohols, free hydroxyl anomeric sugars, aromatic amines and C-protected α-aminoacids.

Chemicals associated with decreases in the incidence of mononuclear cell leukemia in the Fischer rat.

A significant treatment-related decrease in the incidence of mononuclear cell leukemia (MCL) was identified in Fischer-344/N rats for 20 chemicals tested in the National Toxicology Program's 2-yr carcinogenicity bioassay. Fourteen of the 20 chemicals caused decreases of MCL in both male and female rats; 6 of the 20 caused a significant decrease only in males and a marginal or no decrease in female rats. Seventeen of the chemicals associated with a decrease in MCL had a free aromatic amine or nitro functional groups that could be metabolized to free amines. With 1 exception, all 14 chemicals causing a decrease in MCL in both sexes produced spleen toxicity in the 13-wk studies. Reduced body weight and decreased survival, related either to toxicity or to an increase in other types of lethal neoplasms, did not contribute to the decreases in MCL observed in chemical exposure groups. Thirteen of the 20 chemicals were positive in Salmonella tests, and 15 were associated with increases in neoplasms at other sites in rats and/or mice, suggesting that different metabolites could be responsible for these varied biological effects.

Recycling of flexible polyurethane foams with a low aromatic amine content

The glycolysis process is the basis for a controlled degradation of crosslinked polyurethane for recycling. Flexible water-blown polyurethanes are polymers with repeating urethane and urea groups. When they undergo heating in presence of glycols and selective catalysts, the reaction of these groups leads to products that are liquid at room temperature. The transesterification reaction of the urethane groups, that leads to the formation of new carbamate is faster than that of the urea groups that leads to the formation of carbamates and amines. The carbamates in turn undergo aminolysis due to the amines formed in the glycolysis of the urea groups to give insoluble products. The possibility of transforming the free aromatic amines by means of a reaction with formaldehyde into products with methylol end groups has been studied. At the same time the formation of a solid phase, mainly of urea groups, has been avoided. The use of ethylene glycol (EG) allows the process to be carried out with high polymer/glycol ratio (up to 4:1) even if a biphase product is obtained. The top phase is mainly formed by the polyether polyol from the polymer, the bottom phase is formed by the solution of carbamates, ureas and amines in EG.

Polyamine metabolism in normal and sterile Chrysanthemum morifolium

In normal and sterile Chrysanthemum plants ( Chrysanthemum morifolium) polyamine conjugate appeared in the apical meristem before the first observable transformation of the meristem into floral structures. These compounds accumulated upon floral initial and well before floral evocation. In fertile plants ( C. morifolium v. Epidote) spermidine conjugates were predominant during floral initiation whereas in male-sterile plants ( C. morifolium v. Jericho) only putrescine conjugates were detected. In both cases ornithine decarboxylase (ODC) is involved in regulating floral initiation in normal and male-sterile plants. The male-sterile flowers can be distinguished by their lack of free aromatic amines and aromatic amine conjugates. In fertile flowers diamine oxide (DAO) followed the same pattern as ODC. In male-sterile flowers DAO activity did not parallel the increase in ODC activity.

42] Aromatic amine-hemoglobin adducts

Publisher Summary This chapter deals with aromatic amine-hemoglobin adducts. Human exposure to aromatic amines has multiple documented and potential sources, including tobacco smoke inhalation, workplace contamination, pesticide residues in food, airborne nitroaromatic compounds, and enterobacterial reduction of dyes. Many aromatic amines, perhaps most of the ones with one- and two-ring structures, form hemoglobin adducts through a process of hepatic metabolic oxidation to an aryl hydroxylamine followed by heme-mediated oxidation to a nitrosoarene and reaction with a cysteine sulfhydryl group. In human hemoglobin, 4-aminobiphenyl forms a single stable adduct with β93(F9) cysteine, which has been fully characterized as a sulfinic amide. Adduct levels of 4-aminobiphenyl in persons undergoing smoking withdrawal decline nearly as expected on the basis of normal hemoglobin turnover. Other studies with experimental animals, though, indicate that amine adducts or amine-adducted hemoglobin can be removed from circulation more rapidly than normal hemoglobin. Overall conversion of aromatic amines to adducts can be very high, as much as 10% of intake, making these compounds very amenable to biomonitoring. The adducts are readily hydrolyzed to regenerate free aromatic amines, which can be determined by gas chromatographic analysis. The most sensitive and selective detection, which is necessary for studies, such as those involving tobacco smoke exposure, is negative-ion chemical ionization mass spectrometry.

Chemical reduction of FD&C Yellow No. 5 to determine combined benzidine

Data are presented suggesting the presence of the aromatic amine benzidine as a combined impurity in the regulated color additive FD&C Yellow No. 5. The benzidine exists as an azo-dye constituent that forms from free benzidine impurities introduced during the manufacture of the color additive. The presence of combined benzidine is ascertained by sodium dithionite reduction of the azo bonds in the commercial color additive. The resulting reduction products are extracted with chloroform, and the liberated benzidine is determined by high-performance liquid chromatography (HPLC). The levels of benzidine determined by HPLC exceed those levels of benzidine accounted for by direct determination of free aromatic amines in the unreduced color.

Predicting azo dye toxicity

Abstract Literature regrading azo dye carcinogenicity was examined to establish, if possible, guidelines to predict the human health risks of new azo dyes. Three different mechanisms for azo dye carcinogenicity were identified, all involving metabolic activation to reactive electrophilic intermediates that covalently bind DNA. In the order of decreasing number of published references, these mechanisms are Azo dyes that are toxic only after reduction and cleavage of the azo linkage to give aromatic amines, mostly via intestinal anaerobic bacteria. The aromatic amines are met‐abolically oxidized to reactive electrophilic species that covalently bind DNA. Azo dyes with structures containing free aromatic amine groups that can be meta‐bolically oxidized without azo reduction. Azo dyes that may be activated via direct oxidation of the azo linkage to highly reactive electrophilic diazonium salts. Each mechanism may be compound specific, thus azo toxicity is probably caused by more than one mechanism. Although i...

Evaluation of azo food dyes for mutagenicity and inhibition of mutagenicity by methods using Salmonella typhimurium

The mutagenicity of 4 azo dyes (FD&C Yellow No. 5, FD&C Yellow No. 6, FD&C Red No. 40 and amaranth) that are widely used to color food has been evaluated. 4 different methods were used: (1) the standard Ames plate-incorporation assay performed directly on the dyes in the absence of S9 and in the presence of rat- or hamster-liver S9; (2) application of the standard plate assay to ether extracts of aqueous solutions of the dyes; (3) a variant of the standard assay, using hamster liver S9, preincubation, flavin mononucleotide (FMN) and other modifications designed to facilitate azo reduction; and (4) reduction of the dyes with sodium dithionite, followed by ether extraction and the standard plate assay. Assays that include chemical reduction (methods 3 and 4) were included because azo compounds ingested orally are reduced in the intestine with the release of free aromatic amines. No mutagenic activity was seen for any of the azo dyes tested by using the standard Ames plate assay (method 1). Ether extracts of some samples of FD&C Yellow No. 6, FD&C Red No. 40 and amaranth were active (method 2), but only at high doses, generally 250 mg-equivalents or more per plate. These results indicate the presence of low level of ether-extractable mutagenic impurities. The FMN preincubation assay (method 3) gave negative results for all dye samples tested. Most batches of FD&C Red No. 40 tested had mutagenic activity that was detectable when the ether extract of less than 1 mg of dithionite-reduced dye was plated in the presence of S9 (method 4). This finding implies that an impurity in these samples of FD&c Red No. 40 can be reduced to yield an ether-extractable mutagen. Dithionite-reduced samples of FD&C Yellow No. 6 and amaranth showed ether-extractable mutagenic activity only at much higher doses than those at which activity was seen with most dithionate-reduced samples of FD&C Red No. 40 (method 4). FD&C Yellow No. 5 showed no mutagenic activity with this method. Mutagenic activity was not detected when FD&C Red No. 40 was tested by using the azo reduction preincubation assay with FMN (method 3). The failure to detect the activity of the mutagenic reduction product in the FMN azo reduction assay may be explained by the observation that addition of FD&C Red No. 40 interferes with the detection of the mutagenic activity of the extract of dithionite-reduced dye. In fact, all 4 azo food dyes inhibited the mutagenic activity of both the FD&C Red No. 40 reduction product and N-(2-fluorenyl)acetamide.

Determination of p-cresidine in FD&C red no. 40 by the diazotization and coupling procedure followed by reversed-phase high-performance liquid chromatography

The free aromatic amine p-cresidine is determined at low ppb (10 9) levels in the regulated color additive FD&C Red No. 40. The determination involves chloroform extraction of p-cresidine and other unsulfonated impurities from the color additive, followed by diazotization of the aromatic amines and coupling with the disodium salt of 3-hydroxy-2,7-naphthalenedisulfonic acid (R-salt). The coupling products are then determined by reversed-phase high-performance liquid chromatography. Calibration is performed in the presence of the color additive by using the external standard method. The identity of the p-cresidine coupling product is confirmed by obtaining a UV-VIS spectrum of the eluting solute. The presence of aniline in commercial batches is also confirmed in this manner by using 4,5-dihydro-5-oxo-l-(4-sulfophenyl)-1H-pyrazole-3-carboxylic acid (pyrazolone-T) as an alternative coupling agent.

Trace analysis of amines and isocyanates using glass capillary gas chromatography and selective detection IV. Determination of free aromatic amines using nitrogen-selective detection

A method for trace analysis of free aromatic amines of special interest in relation to the rubber industry is presented. It involves separation of the amines by high temperature glass capillary gas chromatography on an OV-73 stationary phase, using on-column injection and nitrogen-selective detection. The necessary inertness of the column was achieved by deactivation with octamethylcyclotetrasiloxane. Linear calibration plots were obtained over the range 50–1600 pg and detection limits in the range 10–20 pg.

Diatrizoate Contrast Agents

We have examined the metabolic behavior of several triiodobenzoic acid derivatives because of the observed mutagenicity and cytotoxicity of 3-amino-5-acetamido-2,4,6-triiodobenzoate (I) and 3,5-diamino-2,4,6-triiodobenzoate (II). Measurements were facilitated using iodine-131 (131I)-labeled compounds. Drug retention in rabbits was monitored with a gamma camera. Metabolic products were studied by column and thin-layer chromatography. 3,5-Diacetamido-2,4,6-triiodobenzoate (diatrizoate) was partially deacetylated by liver microsomes to I and II. II was transformed in part to another substance whose structure remains undetermined. About 1% of nominal doses of I, II, and diatrizoate were retained for several days following intracardiac injection in rabbits. The rabbit did not appreciably acetylate I to diatrizoate and converted some of II to a urinary metabolite which was similar to that formed by liver microsomes. I was present in human urine following excretory urography with diatrizoate, but II was not detected. Manufacturers of diatrizoate should further reduce the level of free aromatic amines in preparations of diatrizoate. A method of doing so is reported.