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Hydrogen-bonded aggregates of B(C6F5)3and water are proven as strong Brønsted acid catalysts, which have the advantages of low toxicity and broad compatibility. Sulfoxonium ylides are stable surrogates of diazo compounds, which participate in various reactions due to their versatile reactivity. Based on these characteristics, a strategy for C–N bond or C–C bond construction of aromatic amines with sulfoxonium ylides under metal-free catalytic conditions was established. This method has advantages of mild conditions and excellent yield, which is suitable for the N–H or C–H functionalization of various aromatic amine compounds.

Redox nanozymes have exhibited various applications in recognizing environmental pollutants but not aromatic amines (a type of typical pollutant). Herein, with Cu2+as a node and tryptophan (Trp) as a linker, Cu-Trp as a specific ascorbic acid oxidase mimic was synthesized, which could catalyze ascorbic acid (AA) oxidation to dehydroascorbic acid (DHAA). Alternatively, with other natural amino acids as linkers to synthesize Cu-based nanozymes, such catalytic performances are also observed. The as-produced DHAA could react with o-phenylenediamine (OPD) and its derivatives (2,3-naphthalene diamine (NDA), 4-nitro-o-phenylenediamine (4-NO2–OPD), 4-fluoro-o-phenylenediamine (4-F-OPD), 4-chloro-o-phenylenediamine(4-Cl-OPD), and 4-bromo-o-phenylenediamine(4-Br-OPD)) to form a Schiff base and emit fluorescence. Based on the results, with Cu-Trp + AA and Cu-Arg (with arginine (Arg) as a linker) + AA as two sensing channels and extracted red, green, and blue (RGB) values from emitted fluorescence as read-out signals, a visual sensor array was constructed to efficiently distinguish OPD, NDA, 4-NO2–OPD, 4-F-OPD, 4-Cl-OPD, and 4-Br-OPD as low as 10 μM. Such detecting performance was further confirmed through discriminating binary, ternary, quinary, and senary mixtures with various concentration ratios, recognizing 18 unknown samples, and even quantitatively analyzing single aromatic amine. Finally, the discriminating ability was further validated in environmental waters, providing an efficient assay for large-scale scanning levels of multiple aromatic amines.

In this work, a practical copper-catalyzed multicomponent coupling reaction of primary aromatic amines, rongalite, and alkynes for the direct synthesis of N-aryl propargylamines has been developed. This method could overcome the substrate limitation in A3coupling reactions of primary aromatic amines, formaldehyde, and alkynes. Mechanistic studies revealed that rongalite acts as not only the active C1 unit but also the accelerator to activate the in situ-generated N-arylmethanimines for the coupling reaction with alkynes. This coupling reaction is highly efficient and features a broad substrate scope, as well as utility with scale-up synthesis and converting the corresponding product N-aryl propargylamines into useful heterocyclic skeletons.

The 3d transition metal-catalyzed enantioconvergent radical cross-coupling provides a powerful tool for chiral molecule synthesis. In the classic mechanism, the bond formation relies on the interaction between nucleophile-sequestered metal complexes and radicals, limiting the nucleophile scope to sterically uncongested ones. The coupling of sterically congested nucleophiles poses a significant challenge due to difficulties in transmetalation, restricting the reaction generality. Here, we describe a probable outer-sphere nucleophilic attack mechanism that circumvents the challenging transmetalation associated with sterically congested nucleophiles. This strategy enables a general copper-catalyzed enantioconvergent radical N-alkylation of aromatic amines with secondary/tertiary alkyl halides and exhibits catalyst-controlled stereoselectivity. It accommodates diverse aromatic amines, especially bulky secondary and primary ones to deliver value-added chiral amines (>110 examples). It is expected to inspire the coupling of more nucleophiles, particularly challenging sterically congested ones, and accelerate reaction generality.

Aromatic amines are a class of carcinogenic compounds present in tobacco smoke that are listed on the U.S. Food and Drug Administration (FDA) list of harmful and potentially harmful constituents (HPHCs) in tobacco products and tobacco smoke. The yields of six aromatic amines (1-aminonaphthalene [1-AN], 2-aminonaphthalene [2-AN], 3-aminobiphenyl [3-ABP], 4-aminobiphenyl [4-ABP], ortho-toluidine [o-TOL], and o-anisidine [o-ANI]) in the mainstream smoke from 23 commercial filtered cigars, 16 cigarillos, and 11 large cigars were determined using solid-phase microextraction coupled to gas chromatography triple quadrupole mass spectrometry (SPME headspace GC–MS/MS). The commercial cigars were smoked under the Cooperation Centre for Scientific Research Relative to Tobacco (CORESTA) Recommended Method 64 using a linear cigar smoking machine. The aromatic amine yields in the mainstream smoke from 50 commercial cigars show high levels of variation within and between the products. The average yields of the aromatic amines in the filtered cigars, cigarillos, and large cigars were 108, 371, and 623 ng/cigar for o-TOL; 6, 14, and 22 ng/cigar for o-ANI; 65, 114, and 174 ng/cigar for 1-AN; 25, 59, and 87 ng/cigar for 2-AN; 6, 17, and 27 ng/cigar for 3- ABP; and 8, 11, and 17 ng/cigar for 4-ABP, respectively. The relationships between aromatic amines and (1) total particulate matter (TPM), (2) water-soluble proteins, and (3) water-insoluble proteins were evaluated. We found that the aromatic amines showed a good linear response with TPM on a per cigar basis and showed significant positive correlations with proteins. In addition, the water-insoluble proteins make a greater contribution to the formation of aromatic amines compared to the water-soluble proteins.

Aromatic amines in nature are typically installed with Glu or Gln as the nitrogen donor. Here we report a pathway that features glycyl-tRNA instead. During the biosynthesis of pyrroloiminoquinone-type natural products such as ammosamides, peptide-aminoacyl tRNA ligases append amino acids to the C-terminus of a ribosomally synthesized peptide. First, AmmBCTrpadds Trp in a Trp-tRNA-dependent reaction and the flavoprotein AmmC1then carries out three hydroxylations of the indole ring of Trp. After oxidation to the corresponding ortho-hydroxy para-quinone, AmmBDGlyattaches Gly to the indole ring in a Gly-tRNA dependent fashion. Subsequent decarboxylation and hydrolysis results in an amino-substituted indole. Similar transformations are catalysed by orthologous enzymes from Bacillus halodurans. This pathway features three previously unknown biochemical processes using a ribosomally synthesized peptide as scaffold for non-ribosomal peptide extension and chemical modification to generate an amino acid-derived natural product.

Primary aromatic amines (PAAs) may be found in food contact materials and can potentially migrate from packaging material into the packed foodstuffs. Certain members of this substance class are of particular concern due to their toxicological properties. Legislators and authorities require a risk assessment regarding the transfer of PAAs into food. The evaluation of PAAs’ migration into food relies on migration or extraction tests using aqueous and acidic food simulants or solvents. However, PAAs exhibit stability issues in acidic media, which could lead to an underestimation of migration. Therefore, a systematic stability study was conducted for 28 PAAs in 3% acetic acid and water at different storage conditions. Standard solutions of 2 and 10 ng/ml of the amines in these media were prepared and stored under the following conditions: 2 h at 40 °C, 70 °C, and 100 °C, and 10 days at − 20 °C, 4 °C, 20 °C, 40° C, and 60 °C. The test solutions were analyzed using liquid chromatography coupled to mass spectrometry, and recovery was calculated against freshly prepared standard solutions. It was found that several PAAs undergo a loss of recovery under the investigated conditions; 7 of the substances were identified to be the most unstable: 3,3ʹ-dimethoxybenzidine, 3,3ʹ-dimethylbenzidine, 6-methoxy-m-toluidine, 4-methoxy-m-phenylendiamine, 2,6-toluenediamine, benzidine and 2,4-toluenediamine. It was concluded that both time and storage temperature play a pivotal role in the stability of PAAs. The experiments also demonstrated that PAAs exhibit greater stability in water than in 3% acetic acid.

Oxidase-mimicking nanozymes are some of the most important nanozymes, which are investigated in various buffer concentrations. However, buffer concentration-dependent catalytic performance is rarely investigated. Herein, with o-phenylenediamine (OPD) as a substrate, the catalytic performance of Cu-Adenine oxidase mimic (fabricated with Cu2+as an active center and adenine as a ligand) gradually decreases upon Tris–HCl buffer concentration (CTris–HCl) increasing from 10 to 200 mM, exhibiting buffer concentration-dependent catalytic activity. Such buffer concentration-dependent catalytic activity is believed to be because Tris–HCl and OPD competitively bind with Cu-Adenine, leading to differences in catalytic activity. Similarly, with 2,4-dichlorophenol (2,4-DP) as a substrate and 4-aminoantipyrine (4-AP) as a chromogenic agent, the same results are obtained. However, with 2,2′-azino-bis(3-ethylbenzothiazoline-6-sulfonic acid) (ABTS) and 3,3′,5,5′-tetramethylbenzidine (TMB) as substrates, the catalytic oxidation cannot be observed at CTris–HCl≥ 50 mM. Tris–HCl and substrate competitively binding with Cu-Adenine produces buffer concentration-dependent catalytic performance. Subsequently, substrates are successfully expanded to other aromatic amines (p-phenylenediamine (PPD), 1,5-naphthalenediamine (1,5-NDA), 1,8-naphthalenediamine (1,8-NDA)) and phenols (phenol, 3-cresol, 1-naphthol). Based on the results, with 50 and 150 mM Tris–HCl buffer solutions as sensing channels, a Cu-Adenine-based colorimetric sensor array is constructed for discriminating four representative aromatic amines (OPD, PPD, 1,5-NDA, 1,8-NDA) and four phenols (2,4-DP, phenol, 3-cresol, 1-naphthol) as low as 50 μM. The performance is further validated through accurately identifying binary, quaternary, and even senary and octonary mixtures. Finally, the designed sensor array is successfully applied for identifying eight representative aromatic amines and phenols in river water, seawater, and sewage water, presenting great potential and valuable applications for large-scale scanning levels of aromatic amines and phenols in water samples.

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