Oxidation Of Aromatic Amines Research Articles

Optimization studies on laccase activity of Proteus mirabilis isolated from treatment sludge of textile industry factories : Optimization of laccase activity of Proteus mirabilis.

Laccase is an exothermic enzyme with copper in its structure and has an important role in biodegradation by providing oxidation of phenolic compounds and aromatic amines and decomposing lignin. The aim of this study is to reach maximum laccase enzyme activity with minimum cost and energy through optimization studies of Proteusmirabilis isolated from treatment sludge of a textile factory. In order to increase the laccase enzyme activities of the isolates, medium and culture conditions were optimized with the study of carbon (Glucose, Fructose, Sodium Acetate, Carboxymethylcellulose, Xylose) and nitrogen sources (Potassium nitrate, Yeast Extract, Peptone From Soybean, Bacteriological Peptone), incubation time, pH, temperature and Copper(II) sulfate concentration then according to the results obtained. Response Surface Method (RSM) was performed on six different variables with three level. According to the data obtained from the RSM, the maximum laccase enzyme activity is reached at pH 7.77, temperature 30.03oC, 0.5g/L CuSO4, 0.5g/L fructose and 0.082g/L yeast extract conditions. After all, the laccase activity increased 2.7 times. As a result, laccase activity of P. mirabilis can be increased by optimization studies. The information obtained as a result of the literature studies is that the laccase enzymes produced in laboratory and industrial scale are costly and their amounts are low. This study is important in terms of obtaining more laccase activity from P.mirabilis with less cost and energy.

Tandem Electrochemical Oxidation of Polycyclic Aromatic Amines Towards Carbazoles and Phenazine-based Aza-helicenes.

Experimental and theoretical study of the regioselectivity and mechanism of polycyclic aromatic amine (PAA) electrochemical oxidation is important for designing nitrogen doped large π-conjugated functional molecules. Herein, we used binary-, ternary-, and quaternary-fused PAAs as electro-oxidative reaction substrates to investigate the yield changes of carbazole and phenazine based aza-helicene other than oligomers, which were obtained through pyrrole and pyrazine annulation pathways. Combined with the restrained electrostatic potential (RESP) and steric hindrance factor analysis of the substrate, the electron spin density distribution of free radical resonance hybrid and the spin population analysis of the atoms in the structure of each free radical tautomer indicate that the degree of delocalized dispersion of N free radical and the resulting change in the spin density distribution of C free radical tautomers determine the reaction regioselectivity. The potential charge of the K-region, Bay-region, and L-region adjacent to the C(α)-C(β1) bond is higher than that of other regions within the molecule, and the charge in these high RESP regions tends to delocalize more strongly toward electron-deficient N free radicals. Thus, the activity of N-C(α)-C(β1) region is increased, which supports the proposed free radical addition and free radical coupling mechanism for the electro-oxidative reaction of PAA.

Novel chromatic reaction based on the redox reaction between tertiary aromatic amines and gold(Ⅲ) or cerium(Ⅳ)

Abstract Herein, a novel chromatic reaction based on the oxidative self-coupling of tertiary aromatic amines and driven by a redox reaction with gold(III) or cerium(IV) is developed. The dimers resulting from the oxidation of tertiary aromatic amines with gold(III) or cerium(IV) show colors depending on their chemical structures. Substituting a hydrogen atom on the aromatic ring with a methyl or methoxy group induces a bathochromic shift in the color developed via oxidation. This redox reaction is highly selective for gold(III) and cerium(IV) because of their high redox potentials and complexation abilities with tertiary aromatic amines, thus suggesting the development of a selective analytical method for gold(III) and cerium(IV). Cyclic voltammograms and ultraviolet–visible light absorption spectra confirm that the oxidative coupling of tertiary aromatic amines develops color. The addition of reductants, such as l-ascorbic acid, degrades the color of the resultant colored species, thus indicating that the quinoid structure of the colored species caused color development. Thus, the developed redox reaction of tertiary aromatic amines with gold(III) or cerium(IV) provides a new chromogenic platform for determining gold(III), cerium(IV), and ascorbic acid.

N-dealkylation of amines during water disinfection – Revealing a new direction in the formation of disinfection by-products

Among numerous disinfection by-products (DBP) forming during aqueous chlorination nitrogen containing species are of special concern due to their toxicological properties. Nevertheless, corresponding reaction products of these natural and anthropogenic compounds are not sufficiently studied so far. An interesting reaction involves dealkylation of the substituted amine moiety. Here we present the results of the comparative study of one-electron oxidation and aqueous chlorination of several aliphatic and aromatic amines. The reaction products were reliably identified with gas chromatography – high resolution mass spectrometry (GC-HRMS), high pressure liquid chromatography – electrospray ionization high resolution mass spectrometry HPLC-ESI/HRMS), and electrochemistry - electrospray ionization high resolution mass spectrometry (EC-ESI/HRMS). Certain similarities dealing with the formation of the corresponding aldehydes and substitution of alkyl groups at the nitrogen atom for hydrogen were shown for the studied processes. The mechanism of the substituted amines’ aqueous chlorination involving one-electron oxidation is proposed and confirmed by the array of the observed reaction products. Alternative reactions taking place in conditions of aqueous chlorination, i.e. aromatic electrophilic substitution, may successfully compete with dealkylation and produce major products.

Anode Catalysts for Electrocatalytic Alcohol Oxidation Coupled to CO2 Reduction in Continuous-Flow Electrolyzers

Thanks to the intense scientific interest, the field of CO2 electrolysis witnessed remarkable progress (industrially relevant partial current densities, selective electrocatalysts towards small molecule products, multi-cell stacks, etc.) in the past decade. However, despite all these efforts, the energy efficiency of CO2 electrolyzers is still relatively low, which is rooted in the large cell voltages. A reason behind this is that the kinetically sluggish water oxidation (OER) is performed at the anode in parallel with CO2 reduction (CO2RR) at the cathode. This issue can be circumvented by coupling CO2RR with alternative anode processes, resulting in smaller cell voltage (better energy efficiency) along with the possible generation of products at the anode with high market value. Thus, maximizing the potential of utilizing waste carbon sources to generate value-added products. Such alternative reactions include, for example, the electrocatalytic oxidation of chloride ions, aliphatic and aromatic alcohols, amines, urea, hydrazine, and numerous biomass-derived substances such as 5-(hydroxymethyl)furfural, sorbitol, etc.In this study, CO2RR to CO was driven at the cathode, and the electrocatalytic oxidation of glycerol (GOR) was performed at the anode of a small (1 cm2 active surface area) microfluidic electrolyzer cell. Ir black was replaced by carbon-supported Pt nanoparticles, while Ag nanoparticles were used as the cathode catalyst. During our experiments, we identified four main factors influencing the GOR activity and selectivity: i) the quality and quantity of the used ionomer, ii) the electrolyte flow rate, iii) glycerol concentration, and iv) the applied anode potential. The latter was particularly important since Pt showed the highest activity toward GOR in a potential window where its surface starts to oxidize. The formation of a continuous oxide layer has to be avoided since it inhibits the alcohol oxidation reaction. By setting optimal conditions, a close to 100% Faradic efficiency (FE) toward CO formation on the cathode and between 70-80% FE toward GOR was achieved above 200 mA cm-2 total current density. The amount of the formed products were tracked by mass spectrometry, gas-, and high-performance liquid chromatography, and nuclear magnetic resonance spectroscopy. Dihydroxyacetone, glycerate, glycolate, oxalate, tartronate, formate, and lactate were identified as GOR products. The missing charge was attributed to the formation and a small amount of CO2. To improve the stability and selectivity of Pt in GOR, semipermeable metal oxide layers were introduced to the top of the catalyst layer. The thin films were synthesized by electrodeposition in different thicknesses. Based on our measurements, a set of criteria were defined regarding the composition of the anode catalyst layer (ionomer, co-catalyst overlayer, etc.), the composition of the electrolyte solution, and the applied electrochemical protocol to allow stable and selective GOR at high achievable current densities.

Purification and characterization of novel manganese peroxidase from Trichoderma parestonica and its bio-conversion study of toxic arylamine

Trichoderma parestonica is a novel source of manganese peroxidase (MnP), [E.C.1.11.1.13] enzyme. The following was the sequence in which T. parestonica induced the production of MnP in the liquid culture medium: rice husk, corncob, sawdust, coir-dust and dried luffa on days 3, 4, 5, 2 and 3, respectively. The molecular weight of the enzyme was found to be 45kDa, determined from SDS-PAGE analysis which was further confirmed by mass analysis and was found to be 51.9kDa. Enzyme characterization parameters like optimum pH, temperature, Km, Kcat and catalytic efficiency are 5, 20ᵒC, 0.014mM (for Mn2+) and 0.028mM (for H2O2), 23.9 S-1 and 1.7 μM-1 S-1 respectively. Effect of various metal ions, such as bivalent Copper(Cu), Cobalt(Co), Mercury(Hg), Nickel(Ni), Cadmium(Cd), trivalent Chromium(Cr), Iron(Fe), Tetra-valent cerium(Ce), Penta-valent vanadium(V) and hexavalent molybdenum(Mo) the enzyme-catalyzed steady-state velocity was studied. The inhibition constant and nature of inhibition by these metal ions were determined. In the current investigation, MnP catalytic activities demonstrated that it could effectively catalyze the oxidation of phenols, aromatic amines and wastewater treatment. This communication suggested potential pathways for aromatic amine bioconversion mediated by MnP

Co(OAc)2/TBHP as a Highly Active Catalytic System for the Selective Oxidation of Aromatic Amines to Nitro Derivatives

AbstractAn efficient cobalt-catalyzed protocol for the selective oxidation of anilines using a combination of inexpensive tert-butyl hydroperoxide and Co(OAc)2·4H2O without any ligand has been developed, providing the nitroarene products in good to excellent yields (up to 96%).

Valence-Engineered Oxidase-Mimicking Nanozyme with Specificity for Aromatic Amine Oxidation and Identification.

Oxidase-mimicking nanozymes with specificity for catalyzing oxidation of aromatic amines are of great significance for recognition of aromatic amines but rarely reported. Herein, Cu-A nanozyme (synthesized with Cu2+ as a node and adenine as a linker) could specifically catalyze oxidation of o-phenylenediamine (OPD) in Britton-Robinson buffer solution. Such a specific catalytic performance was also corroborated with other aromatic amines, such as p-phenylenediamine (PPD), 1,5-naphthalene diamine (1,5-NDA), 1,8-naphthalene diamine (1,8-NDA), and 2-aminoanthracene (2-AA). Moreover, the presence of salts (1 mM NaNO2, NaHCO3, NH4Cl, KCl, NaCl, NaBr, and NaI) greatly mediated the catalytic activity with the order of NaNO2 < blank ≈ NaHCO3 < NH4Cl ≈ KCl ≈ NaCl < NaBr < NaI, which was due to anions sequentially increasing interfacial Cu+ content via anionic redox reaction, while the effect of cations was negligible. With the increased Cu+ content, Km decreased and Vmax increased, indicating valence-engineered catalytic activity. Based on high specificity and satisfactory activity, a colorimetric sensor array with NaCl, NaBr, and NaI as sensing channels was constructed to identify five representative aromatic amines (OPD, PPD, 1,5-NDA, 1,8-NDA, and 2-AA) as low as 50 μM, quantitatively analyze single aromatic amine (with OPD and PPD as model analysts), and even identify 20 unknown samples with an accuracy of 100%. In addition, the performance was further validated through accurately recognizing various concentration ratios of binary, ternary, quaternary, and quinary mixtures. Finally, the practical applications were demonstrated by successfully discriminating five aromatic amines in tap, river, sewage, and sea water, providing a simple and feasible assay for large-scale scanning aromatic amine levels in environmental water samples.

Studies on the Oxidation of Aromatic Amines Catalyzed by Trametes versicolor Laccase.

The bio-oxidation of a series of aromatic amines catalyzed by T. versicolor laccase has been investigated exploiting either commercially available nitrogenous substrates [(E)-4-vinyl aniline and diphenyl amine] or ad hoc synthetized ones [(E)-4-styrylaniline, (E)-4-(prop-1-en-1-yl)aniline and (E)-4-(((4-methoxyphenyl)imino)methyl)phenol]. At variance to their phenolic equivalents, the investigated aromatic amines were not converted into the expected cyclic dimeric structures under T. versicolor catalysis. The formation of complex oligomeric/polymeric or decomposition by-products was mainly observed, with the exception of the isolation of two interesting but unexpected chemical skeletons. Specifically, the biooxidation of diphenylamine resulted in an oxygenated quinone-like product, while, to our surprise, in the presence of T. versicolor laccase (E)-4-vinyl aniline was converted into a 1,2-substited cyclobutane ring. To the best of our knowledge, this is the first example of an enzymatically triggered [2 + 2] olefin cycloaddition. Possible reaction mechanisms to explain the formation of these products are also reported.

PURIFICATION AND CHARACTERIZATION OF LACCASE FROM ARTHROGRAPHIS KSF2

Laccases are blue copper oxidases (E.C. 1.10.3.2 benzenediol: oxygen oxidoreductase) that catalyze the one-electron oxidation of phenolics, aromatic amines, and other electron-rich substrates with the concomitant reduction of O2 to H2O. They are currently seen as highly interesting industrial enzymes because of their broad substrate specificity. An ascomycetes strain, Arthrographis KSF2 was isolated and enzyme was purified and characterized. Laccase activity was determined using ABTS as substrate. Laccase was purified by ion-exchange and gel filtration chromatography. The purified laccase showed a molecular weight of 55 kDa and pI of 5.5 when analyzed by 2-D PAGE. The purified enzyme was even stable at pH 11 and it was observed that there was 74.4% retention of activity at pH 11 after 24hrs. The K(m) and V(max) values are 15 (μM) and 21.9 (μmol/min), respectively, with ABTS as substrate. The effect of 5mM metal ions such as Mn2+, Mg2+, Na+, Ca2+, Fe2+, Zn2+ and Cu2+ was estimated after incubating the enzyme with the metal ion for 5 min. It was observed that FeCl3 inhibited the laccase activity to the maximum (70.5%) whereas the enzyme was least inhibited by MnSO4 (21%). It was observed that even CuSO4 inhibited the laccase activity in 5 mM concentration. There was 100% denaturation by 1% SDS in 10 min whereas only 8% denaturation was observed by Tween 20. Tween 80 denatured 21% enzyme and Triton X 100 denatured 25% of the total enzyme. The purified laccase on UV-Vis analysis did not show the characteristic laccase peak at 600 nm and so it was confirmed as a typical yellow laccase.

Electrocatalytic oxidation of aromatic amine (4-aminobiphenyl): Kinetics and transformation products with mechanistic approach.

Electrocatalytic oxidation (EO) of carcinogenic 4-aminobiphenyl (4-ABP) aromatic amine was performed using Ti-RuO2 anodes. Current (I), pH, electrolysis time (t), and 4-ABP initial concentration (Co ) were selected as EO parameters, and their effects on %4-ABP removal (R1 ) and energy consumed (R2 ) were studied. Experimental design, parameters optimization, and their interaction with responses R1 and R2 were performed using response surface methodology. At optimized parameters, %TOC removal and 4-BP mineralization current efficiency (%MCE) were assessed to evaluate the potential of Ti/RuO2 anodes towards 4-ABP mineralization. Simultaneous TOC and 4-ABP degradation kinetics were also studied to evaluate the competition in 4-ABP mineralization and degradation. Further, UPLC-Q-TOF-MS analysis was performed to identify the 4-ABP transformation products during the EO, and a mechanism describing the EO transformation was proposed. At optimum parameters (I = 1.2A; pH = 4.0; t = 30min; Co = 30 ppm), responses were found to be R1 = 60.25%; R2 = 2.49 kWh/g of 4-ABP removed. %TOC removal and %MCE were 52.4% and 34.2%, respectively. PRACTITIONER POINTS: 4-Aminobiphenyl electro-oxidation (EO) was explored using Ti/RuO2 anode. Achieved 34.2% mineralization current efficiency, 52.4% TOC and 61.3% TKN removal. Three electro-oxidation transformation products of 4-ABP were detected. 4-Aminobiphenyl was found degrading at ≈1.6 times higher rate than TOC A plausible EO transformation pathway and mechanism was proposed.

Catalytic selective oxidation of aromatic amines to azoxy derivatives with an ultralow loading of peroxoniobate salts

Tartaric acid-coordinated peroxoniobate salts demonstrate an exceptionally high TOF value (up to 4435 h−1) even at an ultralow catalyst loading for the oxidation of aromatic amines to azoxy compounds under green and very mild conditions.

Copper‐Catalyzed Cascade N‐Dealkylation/N‐Methyl Oxidation of Aromatic Amines by Using TEMPO and Oxygen as Oxidants

AbstractA novel tandem N‐dealkylation and N‐methyl aerobic oxidation of tertiary aromatic amines to N‐arylformamides using copper and TEMPO has been developed. This methodology suggested an alternative synthetic route from N‐methylarylamines to N‐arylformamides.

Rationally constructing of a novel composite photocatalyst with multi charge transfer channels for highly efficient sulfamethoxazole elimination: Mechanism, degradation pathway and DFT calculation

Rational design of highly efficient multi-heterojunction photocatalyst with separated charge transfer channels still remains a challenge. Herein, a novel La2Ti2O7/g-C3N4/AgI photocatalyst is constructed via a facile electrostatic self-assembly plus selective deposition–precipitation method. The results demonstrate that the spatially isolated La2Ti2O7 and AgI are both decorated tightly on g-C3N4 nanosheets and form separated heterojunctions, which provide much more separated charge transfer channels and surface reaction sites. Therefore, the samples exhibit remarkably boosted photodegradation performance for sulfamethoxazole (SMZ). DFT results indicate that the atoms with the most positive and negative value of condensed dual descriptors (CDD) are the mostly vulnerable to reactive species. Aromatic amine oxidation, the cleavage of sulfonamide bond and hydroxylation of aromatic rings are mainly SMZ degradation pathways. This study provides a new insight for the guideline of rational design/development of new multicomponent photocatalysts for potential application on treatment of emerging pollutants in waters.

Metal-Free Deoxygenation of Amine N-Oxides: Synthetic and Mechanistic Studies.

We report herein an unprecedented combination of light and P(III)/P(V) redox cycling for the efficient deoxygenation of aromatic amine N-oxides. Moreover, we discovered that a large variety of aliphatic amine N-oxides can easily be deoxygenated by using only phenylsilane. These practically simple approaches proceed well under metal-free conditions, tolerate many functionalities and are highly chemoselective. Combined experimental and computational studies enabled a deep understanding of factors controlling the reactivity of both aromatic and aliphatic amine N-oxides.

Synthesis of Azobenzenes via direct oxidation of Aryl amines using aqueous tert-Butyl HydroPeroxide

A new method for the direct oxidation of aromatic amines to azobenzenes employing aqueous tertiary-butyl hydrogen peroxide and potassium tertiary butoxide as an oxidant and base, respectively is described. The desired products are obtained in good yields. The developed protocol is associated with certain advantages for example free from any metal oxidants.

Substituent Effect on Oxidative Dimerization of Porphyrins

Three-dimensional π-conjugated molecules have received extensive attention in many chemical research areas due to their interesting structure and unique characteristics. In particular, twisted π-conjugated systems have been focused on for potential applications to solution processible organic materials. To date, numerous twisted organic molecules such as twistacenes have been synthesized. Under these situations, we found that oxidation of aromatic amines facilitates construction of twisted π-conjugated molecules. For example, oxidation of beta-amino substituted porphyrins provided three-dimensional porphyrins in excellent yield. Sequential use of amination and oxidation toward 5,10,15,20-tetramesitylporphyrin afforded highly twisted porphyrin oligomers. For this reaction, structures of the dimers proved dependent on the meso-substituents. This time, we investigated the substituent effect on the dimerization reactions. Introduction of more bulky substituents at meso-positions on oxidation process provided the corresponding twisted porphyrin dimers with larger twisted angles. In the case of p-tolyl and other aryl substituents without ortho substituents afforded porphyrin dimers with double spirocyclic linkages. The electrochemical analysis revealed the presence of electronic communications between two porphyrin units for the obtained dimers even through the spirocyclic linkages. The central metal also affects the conformations of the dimers. The central Ni(II) metal can be easily removed by treatment of sulfonic acid. Insertion of Zn(II) and Cu(II) metals reduced the twisted angle of the corresponding dimers mainly due to the planar features of the porphyrin units. The presence of magnetic interactions between two porphyrin units were revealed by temperature dependent magnetic susceptibility measurements on SQUID with Cu(II) analogues. In this presentation, we will disclose the structural characterizations of these dimers and would like to show the relationship between electrochemical properties and the conformations of porphyrin dimers.

Aerobic dehydrogenation of amines to nitriles catalyzed by triazolylidene ruthenium complexes with O2 as terminal oxidant.

Pyridyl-substituted mesoionic triazolylidene ruthenium cymene complexes catalyze the oxidation of both aromatic and aliphatic amines to nitriles with high activity and selectivity under benign conditions using dioxygen as the terminal oxidant. Modification on the pyridyl moiety of the ligand scaffold has negligible effect on the catalytic performance, while substituents on the triazolylidene directly affect the catalytic fitness of the metal center, leading to distinct catalytic profiles. Pre-dissociation of the cymene ligand and formation of a solvento analogue further enhances the catalytic activity towards nitrile formation. Variation of reaction conditions provided valuable mechanistic insights and resulted in a highly efficient protocol for nitrile formation with maximum turnover numbers around 10 000. The turnover frequency reaches up to 400 h-1, providing one of the fastest catalytic systems known to date for this transformation.

Efficient and Selective Oxidation of Aromatic Amines to Azoxy Derivatives over Aluminium and Gallium Oxide Catalysts with Nanorod Morphology

AbstractAluminium oxide and gallium oxide nanorods were identified as highly efficient heterogeneous catalysts for the selective oxidation of aromatic amines to azoxy compounds using hydrogen peroxide as environmentally friendly oxidant. This is the first report of the selective oxidation of aromatic amines to their azoxy derivatives without using transition metal catalysts. Among the tested transition‐metal‐free oxides, gallium oxide nanorods with small dimensions (9–52 nm length and 3–5 nm width) and fully accessible, high surface area (225 m2 g−1) displayed the best catalytic performance in terms of substrate versatility, activity and azoxybenzene selectivity. Furthermore, the catalyst loading, hydrogen peroxide type (aqueous or anhydrous), and the amount of solvent were tuned to optimise the catalytic performance, which allowed reaching almost full selectivity (98 %) towards azoxybenzene at high aniline conversion (94 %). Reusability tests showed that the gallium oxide nanorod catalyst can be recycled in consecutive runs with complete retention of the original activity and selectivity.

Enantioselective Oxidative Coupling of β-Ketocarbonyls and Anilines by Joint Chiral Primary Amine and Selenium Catalysis.

An enantioselective primary amine-catalyzed total N-selective nitroso aldol reaction (N-NA) was achieved through the oxidation of primary aromatic amines to the corresponding nitrosoarenes catalyzed by selenium reagents and 30% H2O2. This protocol provides a facile and highly efficient access to α-hydroxyamino carbonyls bearing chiral quaternary centers under exceedingly mild and green reaction conditions with high chemo- and enantiocontrol.