N-containing Aromatic Compounds Research Articles

One-Pot Production of Cinnamonitriles from Lignin β-O-4 Segments Induced by Selective Oxidation of the γ-OH Group.

The construction of N-containing aromatic compounds from lignin is of great importance to expanding the boundary of the biorefinery and meeting the demand for value-added biorefinery. However, it remains a huge challenge due to the complex lignin structure and the incompatible catalysis for C-O/C-C bond cleavage and C-N formation. Herein, sustainable synthesis of cinnamonitrile derivatives from lignin β-O-4 model compounds in the presence of 2,2,6,6-tetramethylpiperidine oxide (TEMPO), (diacetoxyiodo)benzene (BAIB), and a strong base has been achieved in a one-pot, two-step fashion under transition-metal-free conditions. Mechanistic studies suggest that this transformation starts from selective oxidation of Cγ-OH of the β-O-4 model compound, followed by retro-aldol condensation, resulting in the cleavage of the Cα-Cβ bond to afford veratraldehyde. Whereafter, the aldol condensation reaction allows coupling of veratraldehyde with nitriles to provide cinnamonitriles. With this protocol, 3,4-dimethoxycinnamonitrile and 3,4-dimethoxyphenyl-2-phenylacrylonitrile were synthesized from lignin β-O-4 model compounds and showed good antibacterial or antifungal activity, showcasing the application potential of lignin in pharmaceutical synthesis.

Optimizing extractants selection for efficient separation of phenols and nitrogen-containing heteroaromatics using hydrogen bond interaction strategies

Optimizing extractants selection for efficient separation of phenols and nitrogen-containing heteroaromatics using hydrogen bond interaction strategies

Enhancement of the ORR Activity and Durability of Pt/C by the Modification with Melamine and N-Containing Aromatic Compounds

The ORR activity and durability of Pt catalysts have to be enhanced for the wider spread of PEFCs. We pay special attention to possibility that surface modification of a Pt catalyst increases its ORR activity. On the Pt surface, Pt-OH species is stabilized too much by network structure of water molecules adsorbed there [1]. The overstabilization of Pt-OH impedes the ORR because this species is an intermediate of ORR. Then, we try to enhance the ORR activity by destabilizing Pt-OH. The perturbation of the water network would destabilize Pt-OH. We try to perturbate the water network by adding an external organic compound to enhance the ORR activity.We tested a wide variety of compounds as an enhancer of ORR of Pt. Although most of compounds tested exhibit no influence of inhibitory effects on the ORR, we found that certain kind of N-containing aromatic compounds -melamine (and tetraazaporphyrin)- enhance the ORR activity of Pt catalysts significantly [2-4]. With the addition of melamine, ORR activity at 0.9 V vs. RHE is increased by 1.6 times although the ECSA decreased (Fig. 1). The enhancement of the ORR activity is reasonably ascribed to the destabilization of Pt-OH, judging from the change of cyclic voltammograms of Pt/C after the addition of melamine.This melamine modification method is also applied for another highly active catalyst (Pt/Pd/C core-shell catalyst) to obtain a further activated catalyst. The mass activity of Pt/Pd/C core-shell catalyst increases by 2.4 times after melamine modification and reaches 3600 AgPt -1 at 0.9 V vs. RHE [5].Melamine also enhances the durability considerably. Under an accelerated durability test (ADT) (80 °C, 0.6 V (3s) - 1.0 V (3s), square wave, 10000 cycles), Pt/C undergoes severe degradation; the ECSA significantly decreases because of the increase in the size of Pt nanoparticles (Fig. 1). However, after the ADT in the presence of melamine, the decrease in ECSA is significantly suppressed [6]. This beneficial effect is due to the suppression of the increase in size of Pt nanoparticles. A melamine polymer (poly-melamine sulfonate)-modified Pt/C also exhibits higher durability than unmodified Pt/C [7]. The suppression of Pt-OH by melamine participates in the enhancement of the durability.In this talk, we introduce discovery of melamine as an ORR enhancer, effect of melamine on the ORR activity/durability of Pt/C, and mechanisms of functions of melamine.This paper is based on the results obtained from projects, JPNP20003, commissioned by the New Energy and Industrial Technology Development Organization (NEDO).

The light absorbing and molecule characteristic of PM2.5 brown carbon observed in urban Shanghai

Both brown carbon (BrC) and the non-absorbing components coated on black carbon (BC) aerosols can enhance the light absorption of BC aerosols. BrC is a complicated mixture of organic compounds and not well characterized, which hinders exploring the links between BrC and optical properties. We conducted an in-depth field study on optical properties of ambient aerosols at a monitoring site in Shanghai, China via real-time monitoring and offline analysis. Results showed that BrC caused light absorption coefficients were 3.3 ± 3.3 Mm−1, 2.2 ± 5.0 Mm−1, 1.2 ± 1.2 Mm−1 at λ = 370, 470 and 520 nm, respectively, accounting for 11%, 10%, 6% of the total aerosol absorption for the corresponding wavelengths. A larger proportion of long-chain aliphatic organosulfates (OSs, CnH2n+2O4S, (CH2)nO5S, (CH2)nO6S) with double bond equivalent (DBE) values of 0 or 1 accounted for 5–20% of the light absorption (λ = 365 nm) for soluble brown carbon (BrC), which were dominating for the days with less N-containing aromatic compounds appearing. Furthermore, the structure of CnH2n+2O4S, (CH2)nO5S, (CH2)nO6S were explored using target MS/MS of HPLC-Q-ToF-MS: (CH2)nO5S series, the most abundant family of OSs, were constructed by functionalizing a saturated hydrocarbon with one sulfate and one carbonyl group. CnH2n+2O4S series were oxidized with only one sulfate group in the aliphatic chain R. (CH2)nO6S series were proposed as aliphatic OSs with one ester group. We speculated aliphatic OSs were formed via acid catalyzed perhydrolysis of hydroperoxides derived from long-chain alkanes releasing from diesel fueled vehicles, followed by the reaction with sulfate anion radicals. Therefore, relevant technologies should be further explored to reduce the impacts from vehicle emissions.

Chromophoric Fingerprinting of Brown Carbon from Residential Biomass Burning

Emissions from residential biomass burning are a significant source of atmospheric brown carbon (BrC). In this study, we used liquid chromatography-photodiode array-high resolution tandem mass spectrometry to investigate the chromophoric fingerprinting of BrC emitted from residential biomass burning. In total, 59 major chromophores were identified, which accounted for 49–85% of the total light absorption of BrC (averaged between 300 and 500 nm) for different samples. These chromophores include furans, lignin pyrolysis products, coumarins, flavonoids, stilbenes, N-containing aromatic compounds, and unsubstituted or oxygenated polycyclic aromatic hydrocarbons, of which some are newly reported as BrC species (e.g., stilbenes and substituted phenyl cyanates). Among the chromophores identified, seven are common to all samples while some are specific to certain biofuel or burning conditions. For instance, 3,3′-dimethoxyquercetin from wheat burning, p-hydroxybenzaldehyde and apigenin from maize smoldering, 4-nitro-2-vinylphenol from maize flaming, and nodakenetin and anthanthrene from wood flaming are specific to the fuel type or burning condition. The identified optical markers will be essential for understanding atmospheric chemical and optical processes of biomass burning BrC in future studies, while the source-specific chromophore profiles developed in this study are a prerequisite for apportioning the biofuel types and burning conditions, which is a key for estimating source-specific radiative forcing.

Chemical composition, structures, and light absorption of N-containing aromatic compounds emitted from burning wood and charcoal in household cookstoves.

N-containing aromatic compounds (NACs) are an important group of light-absorbing molecules in the atmosphere. They are often observed in combustion emissions, but their chemical formulas and structural characteristics remain uncertain. In this study, red oak wood and charcoal fuels were burned in cookstoves using the standard water boiling test (WBT) procedure. Submicron aerosol particles in the cookstove emissions were collected using quartz (Q f ) and polytetrafluoroethylene (PTFE) filter membranes positioned in parallel. A back-up quartz filter (Q b ) was also installed downstream of the PTFE filter to evaluate the effect of sampling artifact on NACs measurements. Liquid chromatography-mass spectroscopy (LC-MS) techniques identified seventeen NAC chemical formulas in the cookstove emissions. The average concentrations of total NACs in Q b samples (0.37 ± 0.31 - 1.79 ± 0.77 μg m-3) were greater than 50% of those observed in the Q f samples (0.51 ± 0.43 - 3.91 ± 2.06 μg m-3), and the Q b to Q f mass ratios of individual NACs had a range of 0.02 - 2.71, indicating that the identified NACs might have substantial fractions remaining in the gas-phase. In comparison to other sources, cookstove emissions from red oak or charcoal fuels did not exhibit unique NAC structural features, but had distinct NACs composition. However, before identifying NACs sources by combining their structural and compositional information, the gas-particle partitioning behaviors of NACs should be further investigated. The average contributions of total NACs to the light absorption of organic matter at λ = 365 nm (1.10 - 2.57%) in Q f and Q b samples (10.7 - 21.0%) are up to 10 times larger than their mass contributions (Q f 0.31 - 1.01%, Q b 1.08 - 3.31%), so the identified NACs are mostly strong light absorbers. To explain more sample extracts absorption, future research is needed to understand the chemical and optical properties of high molecular weight (e.g., MW > 500 Da) entities in particulate matter.

Water/Methanol-Insoluble Brown Carbon Can Dominate Aerosol-Enhanced Light Absorption in Port Cities.

Light absorption enhancement (Eabs) of black carbon (BC) is a key factor in global climate models and is impacted by brown carbon (BrC) and the lensing effect of coatings. We conducted an in-depth field study on Eabs for ambient aerosols at a monitoring point in Shanghai, China, by real-time aerosol optical property monitoring and high-performance liquid chromatography/diode array detector/quadrupole-time-of-flight mass spectrometry (HPLC/DAD/Q-ToF-MS) analysis. The results showed Eabs at λ = 530 nm caused by the lensing effect was about 1.39 ± 027, accounting for 18.84% of the total light absorption. In this study, BrC is classified as soluble BrC (soluble in both water and methanol) or insoluble BrC (insoluble in both water and methanol). Soluble BrC accounted for 13.68 ± 11.15% of the total aerosol light absorption. For the first time, we concluded that insoluble BrC can contribute more than 60 and 97% of total aerosol and BrC light absorption in port cities, respectively. The molecular analysis of soluble BrC identified N-containing aromatic compounds (4-nitrophenol, 4-nitrocatechol, methyl nitrophenol, methyl nitrocatechols, and nitro-1-naphthol) commonly observed in biomass burning emissions or biomass burning-impacted atmospheres. A series of components (C16H26O3S, C17H28O3S, C18H30O3S, and C19H32O3S) were determined to be emissions from nearby cargo ships filled with heavy fuel oil (HFO), which further confirmed that insoluble BrC emitted from cargo ships could be the largest contributor to Eabs. This study confirms the global significance of evaluating HFO used in port cities in climate models. The control measures of cargo ship emission should be considered for the related environmental and health issues in port cities.

Composition and light absorption of N-containing aromatic compounds in organic aerosols from laboratory biomass burning.

This study seeks to understand the compositional details of N-containing aromatic compounds (NACs) emitted during biomass burning (BB) and their contribution to light-absorbing organic carbon (OC), also termed brown carbon (BrC). Three laboratory BB experiments were conducted with two U.S. pine forest understory fuels typical of those consumed during prescribed fires. During the experiments, submicron aerosol particles were collected on filter media and subsequently extracted with methanol and examined for their optical and chemical properties. Significant correlations (p < 0.05) were observed between BrC absorption and elemental carbon (EC)/OC ratios for individual burns data. However, the pooled experimental data indicated that the BB BrC absorption depends on more than the BB fire conditions as represented by the EC/OC ratio. Fourteen NAC formulas were identified in the BB samples, most of which were also observed in simulated secondary organic aerosol (SOA) from photo-oxidation of aromatic VOCs with NOX. However, the molecular structures associated with the identical NAC formula from BB and SOA are different. In this work, the identified NACs from BB are featured by methoxy and cyanate groups, and are predominately generated during the flaming phase. The mass concentrations of identified NACs were quantified using authentic and surrogate standards, and their contributions to bulk light absorption of solvent extractable OC were also calculated. The contributions of identified NACs to organic matter (OM) and BrC absorption were significantly higher in flaming-phase samples than those in smoldering-phase samples, and correlated with EC/OC ratio (p < 0.05) for both individual burns and pooled experimental data, indicating that the formation of NACs from BB largely depends on burn conditions. The average contributions of identified NACs to overall BrC absorption at 365 nm ranged from 0.087 ± 0.024 to 1.22 ± 0.54%, 3 - 10 times higher than their mass contributions to OM (0.023 ± 0.0089 to 0.18 ± 0.067%), so the NACs with light absorption identified in this work from BB are likely strong BrC chromophores. Further studies are warranted to identify more light-absorbing compounds to explain the unknown fraction (> 98%) of BB BrC absorption.

Aromatic formulas in ambient PM2.5 samples from Hong Kong determined using FT-ICR ultrahigh-resolution mass spectrometry.

Many aromatic compounds (e.g., polycyclic aromatic hydrocarbons (PAHs)) found in atmospheric aerosols are toxic and exist in both unsubstituted and substituted forms. Previous studies have mainly concentrated on investigating unsubstituted PAHs, leaving the substituted compounds largely uncharacterized. This study focuses on detection of both unsubstituted and substituted aromatics in ambient aerosol samples using ultrahigh-resolution mass spectrometry. Aerosol samples collected from roadside, urban, and suburban sites in Hong Kong were characterized by Fourier-transform ion cyclotron resonance mass spectrometry (FT-ICR-MS) coupled with atmospheric pressure photoionization (APPI) or electrospray ionization (ESI). In the APPI+ mode, 166 aromatic CH formulas (i.e., formulas containing C and H only and with a double bond equivalent (DBE) of 4 or higher) were determined through molecular formula calculations based on an accurate m/z determination. Among the determined aromatic CH formulas, 141 are possible alkylated monocyclic aromatic hydrocarbon (MAH) or PAH formulas, and account for ≥ 45% of the total intensity by aromatic CH+ formulas. Both APPI+ and ESI+ are effective in detecting nitroaromatics (i.e., CHO2N1 formulas and DBE ≥ 5). The two ionization modes provide complementary formula coverage, with formulas determined by APPI+ extending to higher DBE and those by ESI+ covering higher carbon numbers. Alkylated nitrobenzene compounds are the most abundant among nitroaromatics, and they, together with alkylated nitro-PAHs, account for > 80% of the total intensity of aromatic CHO2N+ formulas, indicating the importance of these compounds in real aerosol samples. Aromatic CHN+ and CHO+ formulas are also determined, confirming the atmospheric presence of some previously reported O- and N-containing aromatic compounds and revealing new possible formulas. The determination of aromatic organic formulas in this study provides useful guidance for future quantitative analysis of hazardous aromatic compounds. Future work is needed to determine the abundance and to study the toxicity of alkylated MAHs and PAHs outside the 16 US EPA priority PAH compounds. Graphical abstract.

Determination of the promoting effect of nano SiO2 and H3PO4@nano SiO2 in the thiocyanation of N-containing aromatic compounds under solvent-free conditions

Silica nanoparticles/ammonium thiocyanate (nano SiO2/NH4SCN) and H3PO4 embedded on nano silica (H3PO4@nano SiO2) in the presence of NH4SCN were found to be effective systems for the thiocyanation of some arylamines and indoles to afford their corresponding thiocyanated adducts at 70°C under solvent-free conditions. The recovery and reusability of nano SiO2 as a prompting system have been investigated. A simple procedure for the synthesis of H3PO4@nano SiO2 has also been represented. In addition, a plausible mechanism of thiocyanation has also been suggested.

Topological and Electronic Structure of Heterocyclic Compounds Adsorbed on Hydrotreating Catalysts

We studied the electronic structure of the adsorption of S- and N-containing aromatic compounds present in crude oils on MoS2 and WS2 clusters by means of all-electron DFT methods. The aim of this work is to understand results related to the hydrotreating catalyst poisoning by quinoline. We studied the adsorption of the organic compounds by flat (π) and perpendicular (σ) adsorption on each cluster catalyst. The calculated adsorption energies indicated that π-adsorption was more favorable over σ-adsorption. In the σ mode, quinoline presented the largest adsorption energy, which led to understand the poisoning of the catalysts. We performed electron localization function (ELF) studies on the molecules adsorbed on a perpendicular orientation. We showed methyl-substituted compounds had a weaker S-{Mo,W} bond due to steric hindrance. Furthermore, atoms-in-molecules (AIM) calculations at the critical points (i.e. {S,N}-{Mo,W} interfaces) revealed a correlation between electron density and Laplacian of the electron density at this region and the adsorption energy. Ellipticity (e) studies revealed structural information of binding at these sites, as well as the competition between S- and N-containing compounds. Similarly, e showed that methyl-containing compounds had a very distinct character than non-substituted ones, thus revealing the importance of steric effects. Analytic tools such as ELF and AIM provide correlations between the experimental observations and properties. We find these studies can be further used to understand other catalytic phenomena. .

Study on temperature dependence of catalytic thermal decomposition of polyamides and polyurethanes mixed with acidic zeolites

Waste electric and electronic equipments (WEEE) and automotive plastic shredder contain nitrogen-containing polymers such as polyamides and polyurethanes. Thermal decomposition of these polymers leads to pyrolysis oil in which unwanted N-containing compounds are also present. Catalytic pyrolysis can be a way to reduce the oil's N-content or to obtain valuable products. We have examined the slow heating rate pyrolysis of zeolite–polyamide and zeolite–polyurethane mixtures by thermogravimetry-mass spectrometry (TG-MS), moreover flash pyrolysis of the mixtures at three different temperatures were carried out by pyrolysis-gas chromatography mass spectrometry (Py-GC/MS). In TG-MS experiments thermal decomposition characteristics of polyamides are hardly affected by the presence of acidic zeolites, nevertheless, MS ion curves show that the nature of the evolved volatile compounds have changed considerably. Similarly different pyrolysis products have been obtained from pure polyurethanes and polyurethane–zeolite mixtures, but polyurethane–zeolite mixtures have noticeably dissimilar thermal behaviour than the pure polymer. Py-GC/MS measurements have revealed that the pyrolysis temperature significantly affects the pyrolysis product distribution of the investigated polymers and also that of their mixtures with acidic zeolites. For zeolite–polyamide-6,6 1:1 mixtures it was concluded that hexanedinitrile is the main pyrolysis product and its predominance is the highest at 500°C. Main pyrolysis products of zeolite–polyamide-6 mixtures of 1:1 ratio are dihydro-azepine isomers. Their amount does not increase over 450°C, however with rising temperature aromatic compounds are also formed. In case of polyurethane–zeolite mixtures the ether and ester segments are decomposed mainly to monomers, while diisocyanate units are converted to N-containing aromatic compounds. The amount of these compounds is varying with temperature, moreover increasing the pyrolysis temperature (450°C or higher) the formation of aromatic hydrocarbons (benzene and naphthalene compounds) and light unsaturated hydrocarbons are favoured. Flash pyrolysis of polyurethane–NH4Y zeolite mixtures indicated that ammonia notably affects the decomposition of polyester segments leading to hexanedinitrile formation at as low temperature as 400°C.

“Turn-on” Fluorescent Detection of 2,5-Di(4'-carboxylphenyl)-1-phenylpyrrole to Amines

Di(4'-carboxylphenyl)-1-phenylpyrrole was firstly successfully synthesized. UV-Vis and fluorescence spectra were employed to study the optical properties of TPP-2COONa at different pH values in aqueous media. The compound is found to weaken fluorescence in acidic state and, however, strengthen fluorescence in base state. The experimental results indicated that the fluorescent emission of TPP-2COOH can be turned-on by ammonia and some water-soluble alkyl amines (triethylamine, isopropylamine, diiso- propylamine). But it remains unchanged upon addition of N-containing aromatic compounds (aniline, pyr- role, and pyridine). Specially, the compound as the fluorescent probe shows the good selectivity and sensi- tivity toward ammonia. Thus, the on-line naked eye detection for amines becomes possible.

Catechol 1,2-dioxygenase isozymes in soil bacteria metabolizing aromatic compounds

Isozymes of catechol 1.2-dioxygenase (CD, EC 1.13.11.1) from 16 bacterial isolates obtained from soil and grown on aniline as a sole source of C and N have been investigated. Most of the isolates examined contained two isozymes. The 16 organisms were divided into three groups on the basis of isozyme patterns; those with two isozymes of equal enzymatic activity; those with two isozymes of differing enzymatic activity; and those with only one enzyme. Other organisms grown on benzamide as a sole source of C and N also possessed two isozymes of this enzyme. These data suggest that isofunctional enzymes of CD are extensively distributed among soil bacteria that participate in biodegrading N-containing aromatic compounds, such as aniline and benzamide.