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Upcycling waste plastic into aromatics presents an attractive strategy to tackle both plastic pollution and energy challenges. However, previous studies often rely on high temperatures, precious metals, and have broad product distributions. In this study, we reported that a Ni/ZSM-5 bifunctional catalyst can directly convert polyethylene (PE) into methylated aromatics with high selectivity under mild conditions, while eliminating the requirement for hydrogen gas and solvents. The liquid yield could attain up to 70.3 %, and the aromatics yield could achieve up to 51.7 %. Over 78.4 % of the aromatics were methylated aromatics including toluene, xylene, and mesitylene. Polymer chains underwent dehydrogenation over Ni and the acid sites in ZSM-5, forming CC bonds. Certain of these bonds evolved into carbenium ions through the process of proton transfer at the acid sites. The optimization of Ni and acid sites enhanced the oligomerization, cyclization, and aromatization process. The extra mesopores created by Ni on the molecular sieve aid in the generation of aromatics. Furthermore, the Ni/ZSM-5 catalyst demonstrated the ability to convert typical commercial grades of PE plastic, such as gloves and bottles, into aromatics with a selectivity of up to 61.1 %. It offers an economically feasible and environmentally friendly upcycling avenue for the circular economy of plastics., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier B.V. All rights reserved.)

Modified atmosphere packaging (MAP) alters the gaseous composition of air surrounding packaged goods to prevent deleterious oxidation associated reactions. MAP has been adopted for the storage of cannabis, though a recent study revealed little difference in terpene content under MAP conditions. Questions regarding its efficacy for preservation of high value compounds like terpenes and cannabinoids lost during postharvest storage remain. The goal of this research is to determine weather N 2 MAP preserves high value compounds of cannabis during its postharvest storage. This experiment followed a completed randomized block design. There were two factors of interest. The first was storage atmosphere (atmospheric or N 2 MAP). The second was storage duration (18, 46, or 74 days). The experiment was then blocked by cannabis chemovar using 5 different chemovars. The concentration of 17 cannabinoids was evaluated through UPLC-UV and 61 volatile terpene compounds through GC-MS. Concentrations were compared over time and between storage treatments. There were no significant differences in total cannabinoids and volatile terpene compounds over time or between storage treatments. Individual cannabinoids Δ 9 -THC, CBG, CBNA, CBC, THCV, and THCVA all increased during storage time while THCA decreased. CBG and THCV only increased under MAP storage. Individual aromatics limonene, β-pinene, α-pinene, camphene, and terpinolene all only decreased during storage under N 2 MAP. Only caryophyllene oxide and α-humulene increased under N 2 MAP storage. β-Myrcene decreased under atmospheric storage, but not under N 2 MAP. While N 2 MAP had no effect on the preservation of total cannabinoids and aromatics during storage, it did influence several individual compounds. CBG, THCV, and α-humulene all increased under N 2 MAP. N2 MAP also maintained the concentration β-myrcene over time, though the preservation of β-myrcene was offset by a decrease limonene. Overall, N 2 MAP was not needed for preservation of most high value compounds but did have an effect of some compounds with reputed therapeutic benefits., Competing Interests: Declarations. Ethics approval and consent to participate: Not applicable. Consent for publication: Not applicable. Competing interests: The authors declare that they have no competing interests., (© 2024. The Author(s).)

Unlike cyclopropanes, the analogous B 2 C species (diboriranes) tend to adopt non-classical Hückel-aromatic structures with bridging moieties R between the boron atoms. The coordination of the thus generated cyclic 2e - π-system to transition metals is completely unexplored. We here report that complexation of non-classical diboriranes cyclo-μ-RB 2 Dur 2 CPh (R=H, SnMe 3 ; Dur=2,3,5,6-tetramethylphenyl) to Fe(CO) 3 fragments allows for the carbonylative ring expansion of the B 2 C ring to either four- or five-membered rings depending on the nature of the BRB 3-center-2-electron bond (3c2e): The H-bridged diborirane (R=H) initially reacts with Fe 2 (CO) 9 to the allylic π-complex with an agostic BH/Fe interaction. Subsequent formal hydroboration of CO from excess Fe 2 (CO) 9 results in the side-on ring expansion under formation of a five-membered B 2 C 2 O ring, coordinated to the Fe(CO) 3 moiety. In contrast, in case of the stannyl-bridged diborirane (R=SnMe 3 ) under the same conditions, CO is added end-on to the B-B bond with the carbon terminus formally inserting into the B 2 Sn 3c2e-bond. The two carbonylative ring expansion products can also be described as nido and closo clusters, respectively, according to the Wade-Mingos rules., (© 2024 The Authors. Angewandte Chemie International Edition published by Wiley-VCH GmbH.)

In this study, we investigated the pyrolysis of cellulose, lignin, phenylalanine and textile wool waste using microscale thermogravimetric analysis (TGA) and a gram-scale fixed bed reactor. The pyrolysis was conducted at 500 °C and 1 bar N 2 , using Al- and Li-doped mesoporous KIL-2 and ZSM-5 catalysts for comparison. Our results show that amorphous Al-KIL-2 catalyst was the most efficient in producing aromatics from cellulose and lignin. This efficiency is attributed to Al-KIL-2 large mesoporosity, wide pore size distribution, and mild acid sites. Additionally, Al-KIL-2 promoted esterification and denitrogenation reactions, indicating its potential application in the pyrolysis of biomass and protein-rich feedstocks. Conversely, the Li-KIL-2 catalyst demonstrated activity primarily in the depolymerisation of cellulose to sugars and promoted ketonisation and alcohol formation. In summary, our findings indicate that Al-KIL-2 is a promising catalyst for efficient aromatic production from biomass.

Given that ethanol can be obtained from abundant biomass resources (e.g., crops, sugarcane, cellulose, and algae), waste, and CO 2 , its conversion into value-added chemicals holds promise for the sustainable production of high-demand chemical commodities. Nonoxygenated chemicals, including light olefins, 1,3-butadiene, aromatics, and gasoline, are some of the most important of these commodities, substantially contributing to modern lifestyles. Despite the industrial implementation of some ethanol-to-hydrocarbons processes, several fundamental questions and technological challenges remain unaddressed. In addition, the utilization of ethanol as an intermediate provides new opportunities for the direct valorization of CO and CO 2 . Herein, the recent advances in the design of ethanol conversion catalysts are summarized, providing mechanistic insights into the corresponding reactions and catalyst deactivation, and discussing the related future research directions, including the exploitation of active site proximity to achieve better synergistic effects for reactions involving ethanol., (© 2024 Wiley‐VCH GmbH.)

In this study, we employed femtosecond Raman-induced Kerr effect spectroscopy to analyze the concentration-dependent intermolecular dynamics in positively or negatively charged aromatics and their neutral analogous aromatics (imidazolium hydrochloride (ImHCl), imidazole (Im), sodium triazolide (NaTr), and triazole (Tr)) in aqueous solutions at 293 K. We also measured their liquid properties, such as density, viscosity, and surface tension, at 293 K, and compared them with their dynamic properties. Furthermore, we performed the quantum chemistry calculations of the target aromatics and some clusters to elucidate their optimized structures, interaction energies, charge populations, and Raman-active normal modes. We characterized the Kerr transients over 2 ps using a triexponential function. The results revealed that the aqueous solutions' intermediate and slow relaxation time constants were linearly proportional to the viscosities. The slopes of the time constants to the viscosity of the aqueous ImHCl solutions were steeper than those of the aqueous Im solutions, whereas the slopes of the aqueous NaTr solutions were milder than those of the aqueous Tr solutions. These findings indicated that the charge of the aromatics in the aqueous solutions affected the coupling parameter between the solute and solvent in the orientational dynamics with different ways. The first moment (M 1 ) of the low-frequency band (< 200 cm -1 ), coming from the intermolecular vibrations, in the difference spectra between the aqueous aromatic solutions and neat water shifted to the high-frequency region as the concentration increased. The M 1 slope to the concentration for the aqueous ImHCl solutions was steeper than that for the aqueous Im solutions. Conversely, the concentration dependence of M 1 for the aqueous NaTr solutions was similar to that for the aqueous Tr solutions. We used the local structures of the target aromatics based on the quantum chemistry calculations to rationally clarify their concentration-dependent intermolecular dynamics in the aqueous solutions., Competing Interests: Declarations. Conflict of interest: The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (© 2024. The Author(s).)

The Kingdom of Saudi Arabia (KSA) is the leading oil-exploring and -exploiting country in the world. As a result, contamination of the environment by petroleum products (mainly hydrocarbons) is common, necessitating strategies for their removal from the environment. Much work has been conducted on bacterial degradation of hydrocarbons in the KSA. This review comprehensively analyzed 43 research investigation articles on bacterial hydrocarbon degradation, mainly polyaromatic hydrocarbons (PAHs) within the KSA. More than 30 different bacterial genera were identified that were capable of degrading simple and complex PAHs, including benzo[a]pyrene and coronene. Different strategies for selecting and isolating these bacterial strains and their advantages and disadvantages were highlighted. The review also discussed the origins of sample inocula and the contributions of various research groups to this field. PAH metabolites produced by these bacteria were presented, and biochemical pathways of PAH degradation were proposed. More importantly, research gaps that could enrich our understanding of petroleum product biodegradation mechanisms were highlighted. Overall, the information presented in this paper will serve as a baseline for further research on optimizing bioremediation strategies in all petroleum-contaminated environments.

It is necessary for the further development of sludge degradative solvent extraction (DSE) to significantly increase the bio-oil yield and adjust its composition. In this study, the effects of MCM-41, HZSM-5, and SSZ-13 on the physical properties, yield, and composition of bio-oil were compared. Results show that all three catalysts effectively promote the conversion of volatiles in the residue to the heavy component (heavy-s). The addition of MCM-41 improved the yieldof both the light component (light-s) and heavy-s. Their yields increased from 8.11% and 20.47% to 14.39% and 29.18%, respectively. Its all-silicon structure and weak acidity have no significant effect on the composition of the bio-oil. HZSM-5 addition increases the light-s yield to 25.58%. Its MFI structure and proper acidity are beneficial to the formation of aromatic hydrocarbons and olefins, while effectively reducing oxygenates. SSZ-13 increases the heavy-s yield to 27.89%, and promoted the formation of nitrogen-containing compounds significantly., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier Ltd. All rights reserved.)

Chitin-derived furans offer a sustainable alternative feedstock for nitrogen appended aromatic compounds. Herein, we address the challenge of using chitin-derived furans, 3-acetamido-5-acetylfuran (3A5AF) and 3-acetamido-5-furfural aldehyde (3A5F), to favour the formation of exo Diels-Alder adducts and 4-acetylaminophthalimides respectively, using a mechanochemical ball-milling technique. Mechanochemical activation is explored through the synthesis of 7-oxa-norbornene backbones with novel substitution pattern from 3A5AF in yields up to 77 % and improved exo:endo selectivity compared to solution-phase reactions. The synthesis of 4-acetylaminophthalimides from 3A5F in yields up to 79 % is also showcased from hydrazone derivatives., (© 2024 The Authors. ChemSusChem published by Wiley-VCH GmbH.)

Petrochemical wastewater is a major industrial source of pollution that produces a variety of toxic organic and inorganic pollutants, naturally present or added during the process. These pollutants are a serious threat to the soil, water, environment, and human being due to their complex and hazardous nature. Glycols such as monoethylene glycol (MEG), diethylene glycol (DEG), triethylene glycol (TEG), and aromatics (BTX-benzene, toluene, and xylene) are the most common organic impurities present in petrochemical wastewater. The objective of this paper is to recover aromatics and water from petrochemical industrial wastewater. The reclamation process is used to remove inorganic impurities such as heavy metals Fe, Zn, Pb, Mn, Al, Ni, As, Cr, Cu, Cd, and K and salts. In the present work, 1% sodium bi-carbonate (NaHCO 3 ) is used to precipitate the inorganic impurities present in the wastewater at 40 °C atmospherically. Aspen Hysys simulation software is used for modeling and simulation for the treatment process using NRTL (non-random-two-liquid) thermodynamic model. The process generated from Aspen Hysys is validated with lab experiments. To support global sustainable development, this study is focused on reducing, reusing, and recycling separation techniques such as centrifuge separation and vacuum distillation have been used. The characterization of regenerated water was performed using ICP-OES (inductively coupled plasma-optical emission spectroscopy) to determine the reduction in heavy metals. It was found that > 99.5% of heavy metals were removed. The regeneration of these aromatics is necessary for economic and environmental reasons so that it can be reused to avoid its disposal in and contamination of natural environments., (© 2024. The Author(s), under exclusive licence to Springer-Verlag GmbH Germany, part of Springer Nature.)

Bioremediation provides an environmentally sound solution for hydrocarbon removal. Although bioremediation under anoxic conditions is slow, it can be coupled with methanogenesis and is suitable for energy recovery. By altering conditions and supplementing alternative terminal electron acceptors to the system to induce syntrophic partners of the methanogens, this process can be enhanced. In this study, we investigated a hydrocarbon-degrading microbial community derived from chronically contaminated soil. Various hydrocarbon mixtures were used during our experiments in the presence of different electron acceptors. In addition, we performed whole metagenome sequencing to identify the main actors of hydrocarbon biodegradation in the samples. Our results showed that the addition of ferric ions or sulphate increased the methane yield. Furthermore, the addition of CO 2 , ferric ion or sulphate enhanced the biodegradation of alkanes. A significant increase in biodegradation was observed in the presence of ferric ions or sulphate in the case of all aromatic components, while naphthalene and phenanthrene degradation was also enhanced by CO 2 . Metagenome analysis revealed that Cellulomonas sp. is the most abundant in the presence of alkanes, while Ruminococcus and Faecalibacterium spp. are prevalent in aromatics-supplemented samples. From the recovery of 25 genomes, it was concluded that the main pathway of hydrocarbon activation was fumarate addition in both Cellulomonas, Ruminococcus and Faecalibacterium. Chloroflexota bacteria can utilise the central metabolites of aromatics biodegradation via ATP-independent benzoyl-CoA reduction. KEY POINTS: • Methanogenesis and hydrocarbon biodegradation were enhanced by Fe 3+ or SO4 2- • Cellulomonas, Ruminococcus and Faecalibacterium can be candidates for the main hydrocarbon degraders • Chloroflexota bacteria can utilise the central metabolites of aromatics degradation., (© 2024. The Author(s).)

Modification of lignin in feedstocks via genetic engineering aims to reduce biomass recalcitrance to facilitate efficient conversion processes. These improvements can be achieved by expressing exogenous enzymes that interfere with native biosynthetic pathways responsible for the production of the lignin precursors. In planta expression of a bacterial 3-dehydroshikimate dehydratase in poplar trees reduced lignin content and altered the monomer composition, which enabled higher yields of sugars after cell wall polysaccharide hydrolysis. Understanding how plants respond to such genetic modifications at the transcriptional and metabolic levels is needed to facilitate further improvement and field deployment. In this work, we acquired fundamental knowledge on lignin-modified poplar expressing 3-dehydroshikimate dehydratase using RNA-seq and metabolomics. The data clearly demonstrate that changes in gene expression and metabolite abundance can occur in a strict spatiotemporal fashion, revealing tissue-specific responses in the xylem, phloem, or periderm. In the poplar line that exhibited the strongest reduction in lignin, we found that 3% of the transcripts had altered expression levels and ~19% of the detected metabolites had differential abundance in the xylem from older stems. The changes affected predominantly the shikimate and phenylpropanoid pathways as well as secondary cell wall metabolism, and resulted in significant accumulation of hydroxybenzoates derived from protocatechuate and salicylate., (© The Author(s) 2024. Published by Oxford University Press on behalf of the Society for Experimental Biology.)

Catalytic co-pyrolysis of two different refinery oily sludge (ROS) samples was conducted to facilitate resource recovery. Non-catalytic pyrolysis in temperatures ranging from 500 to 600°C was performed to determine high oil yields. Higher temperatures enhanced the oil yields up to ~ 24 wt%, while char formation remained unchanged (~ 45%) for S1. Conversely, S2 exhibited a notably lower oil yield (~ 4 wt%) than S1. Pyrolysis oil of S1 consisted of phenolics (~ 50% at 600 °C) whereas hydrocarbons were predominant in S2 oil (~ 80% at 600 °C). Catalytic pyrolysis of S1 did not exhibit a substantial impact on oil yields but the oil composition varied significantly. High hydrocarbons, phenolics, and aromatics were obtained with molecular sieve (MS), metal slag, and ZSM-5, respectively. Catalytic co-pyrolysis of S2 with sawdust (SD) in the presence of MS enhanced the oil yield, and the resulting oil consisted of high hydrocarbons (~ 54%) and aromatics (~ 44%)., (© 2024. The Author(s), under exclusive licence to Springer-Verlag GmbH Germany, part of Springer Nature.)

This work presents the synthesis of N-doped nanoporous carbon materials using the Ionic Liquid (IL) 1-butyl-3-methylimidazolium tricyanomethanide [BMIM][TCM] as a fluidic carbon precursor, employing two carbonization pathways: templated precursor and pyrolysis/activation. Operando monitoring of mass loss during pyrolytic and activation treatments provides insights into chemical processes, including IL decomposition, polycondensation reactions and pore formation. Comparatively low mass reduction rates were observed at all stages. Heat treatments indicated stable pore size and increasing volume/surface area over time. The resulting N-doped carbon structures were evaluated as electrocatalysts for the oxygen reduction reaction (ORR) and adsorbents for gases and organic vapors. Materials from the templated precursor pathway exhibited high electrocatalytic performance in ORR, analyzed using Rotating Ring-Disk electrode (RRDE). Enhanced adsorption of m-xylene was attributed to wide micropores, while satisfactory CO 2 adsorption efficiency was linked to specific morphological features and a relatively high content of N-sites within the C-networks. This research contributes valuable insights into the synthesis and applications of N-doped nanoporous carbon materials, highlighting their potential in electrocatalysis and adsorption processes., (© 2024 The Authors. ChemPlusChem published by Wiley-VCH GmbH.)

Background: The Asian tiger mosquito, Aedes albopictus, is a competent vector for the spread of several viral arboviruses including dengue, chikungunya, and Zika. Several vital mosquito behaviors linked to survival and reproduction are primarily dependent on a sophisticated olfactory system for semiochemical perception. However, a limited number of studies has hampered our understanding of the relationship between the A. albopictus acute olfactory system and the complex chemical world., Results: Here, we performed a qRT-PCR assay on antennae from A. albopictus of differing sex, age and physiological states, and found that AalbOr10 was enriched in blood-fed female mosquitoes. We then undertook single sensillum recording to de-orphan AalbOr10 using a panel of physiologically and behaviorally relevant odorants in a Drosophila 'empty neuron' system. The results indicated that AalbOr10 was activated by seven aromatic compounds, all of which hampered egg-laying in blood-fed mosquitoes. Furthermore, using a post-RNA interference oviposition assay, we found that reducing the transcript level of AalbOr10 affected repellent activity mediated by 2-ethylphenol at low concentrations (10 -4 vol/vol). Computational modeling and molecular docking studies suggested that hydrogen bonds to Y68 and Y150 mediated the interaction of 2-ethylphenol with AalbOr10., Conclusion: We reveal a potential link between aromatics-induced oviposition repellency behaviors and a specific odorant receptor in A. albopictus. Our findings provide a foundation for identifying active semiochemicals for the monitoring or controlling of mosquito populations. © 2024 Society of Chemical Industry., (© 2024 Society of Chemical Industry.)

The complexity of crude oil composition, combined with the fluctuating oxygen level in contaminated environments, poses challenges for the bioremediation of oil pollutants, because of compound-specific microbial degradation of petroleum hydrocarbons under certain conditions. As a result, facultative bacteria capable of breaking down petroleum hydrocarbons under both aerobic and anaerobic conditions are presumably effective, however, this hypothesis has not been directly tested. In the current investigation, Shewanella putrefaciens CN32, a facultative anaerobic bacterium, was used to degrade petroleum hydrocarbons aerobically (using O 2 as an electron acceptor) and anaerobically (using Fe(III) as an electron acceptor). Under aerobic conditions, CN32 degraded more saturates (65.65 ± 0.01%) than aromatics (43.86 ± 0.03%), with the following order of degradation: dibenzofurans > n -alkanes > biphenyls > fluorenes > naphthalenes > alkylcyclohexanes > dibenzothiophenes > phenanthrenes. In contrast, under anaerobic conditions, CN32 exhibited a higher degradation of aromatics (53.94 ± 0.02%) than saturates (23.36 ± 0.01%), with the following order of degradation: dibenzofurans > fluorenes > biphenyls > naphthalenes > dibenzothiophenes > phenanthrenes > n -alkanes > alkylcyclohexanes. The upregulation of 4-hydroxy-3-polyprenylbenzoate decarboxylase (ubiD), which plays a crucial role in breaking down resistant aromatic compounds, was correlated with the anaerobic degradation of aromatics. At the molecular level, CN32 exhibited a higher efficiency in degrading n -alkanes with low and high carbon numbers relative to those with medium carbon chain lengths. In addition, the degradation of polycyclic aromatic hydrocarbons (PAHs) under both aerobic and anaerobic conditions became increasingly difficult with increased numbers of benzene rings and methyl groups. This study offers a potential solution for the development of targeted remediation of pollutants under oscillating redox conditions., Competing Interests: The authors declare that the research was conducted in the absence of any commercial or financial relationships that could be construed as a potential conflict of interest., (Copyright © 2024 Li, Liu, Guo and Dong.)

Plastics are one of the most produced synthetic materials and largest commodities, used in numerous sectors of human life. To upcycle waste plastics into value-added chemicals is a global challenge. Despite significant progress in pyrolysis and hydrocracking, which mainly leads to the formation of pyrolysis oil, catalytic upcycling to value-added aromatics, including benzene, toluene and xylene (BTX), in one step, is still limited by high reaction temperatures (>500°C) and a low yield. We report herein CO 2 -facilitated upcycling of polyolefins and their plastic products to aromatics below 300°C, enabled by a bifunctional Pt/MnO x -ZSM-5 catalyst. ZSM-5 catalyzes cracking of polyolefins and aromatization, generating hydrogen at the same time, while Pt/MnO x catalyzes the reaction of hydrogen with CO 2 , consequently driving the reaction towards aromatization. Isotope experiments reveal that 0.2 kg CO 2 is consumed per 1.0 kg polyethylene and 90% of the consumed CO 2 is incorporated into the aromatic products. Furthermore, this new process yields 0.63 kg aromatics (BTX accounting for 60%), comparing favorably with the conventional pyrolysis or hydrocracking processes, which produce only 0.33 kg aromatics. In this way, both plastic waste and the greenhouse gas CO 2 are turned into carbon resources, providing a new strategy for combined waste plastics upcycling and carbon dioxide utilization., (© The Author(s) 2024. Published by Oxford University Press on behalf of China Science Publishing & Media Ltd.)

Wax is a detrimental byproduct of plastic waste pyrolysis causing challenges upon its release into the environment owing to persistence and potential toxicity. In this study, the valorization of wax materials through conversion into BTEX (i.e., benzene, toluene, ethylbenzene, and xylene) was achieved via catalytic pyrolysis using zeolite-based catalysts. The potential of two types of waxes, spent wax (SW), derived from the pyrolysis of plastic waste, and commercial paraffin wax (PW), for BTEX generation, was investigated. Using HZSM-5, higher yields of oil (54.9 wt%) and BTEX (18.2 wt%) were produced from the pyrolysis of SW compared to PW (32.3 and 14.1 wt%, respectively). This is due to the improved accessibility of lighter hydrocarbons in SW to Brønsted and Lewis acid sites in HZSM-5 micropores, promoting cracking, isomerization, cyclization, Diels-Alder, and dehydrogenation reactions. Further, the use of HZSM-5 resulted in significantly larger yields of oil and BTEX from SW pyrolysis compared to Hbeta and HY. This phenomenon is ascribed to the well-balanced distribution of Brønsted and Lewis acid sites and the identical geometric structure of HZSM-5 micropores and BTEX molecules. The addition of Ga to HZSM-5 further led to 2.24% and 28.30% enhancements in oil and BTEX yields, respectively, by adjusting the acidity of the catalyst through the introduction of new Lewis acid sites. The regeneration of the Ga/HZSM-5 catalyst by removing deposited coke on the spent catalyst under air partially recovered catalytic activity. This study not only offers an efficient transformation of undesirable wax into valuable fuels but also provides an environmentally promising solution, mitigating pollution, contributing to carbon capture, and promoting a healthier and more sustainable environment. It also suggests future research directions, including catalyst optimization and deactivation management, feedstock variability exploration, and techno-economic analyses for sustainable wax conversion into BTEX via catalytic pyrolysis., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2023 Elsevier Ltd. All rights reserved.)

To address the challenging issues of waste plastic pollution and petroleum shortage, we report herein a pulse pressurized catalytic pyrolysis process where polyethylene is continuously converted into aromatics using HZSM-5 catalyst incorporated with hydrated SiO 2 . Pressurization improves the activity of single-pulse pyrolysis of polyethylene by 14.42%. In contrast to the linear decrease of BTEXS relative yield with a K value of - 0.23 under non-pressurized conditions, pressurization results in a notable stability in the latter stage, characterized by a K value of only - 0.063. Comprehensive catalyst characterization demonstrates that pressurization promotes the release of water from hydrated SiO 2 , enabling HZSM-5 to effectively undergo dealumination and obtain suitable acidity and pore structure, and ultimately enhancing the resistance to carbon deposition. In summary, pressurization improves both pyrolysis activity and catalysis stability, offering a promising strategy for the high-value utilization of waste plastics., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2023 Elsevier B.V. All rights reserved.)

Importance: There is economic and environmental interest in generating commodity chemicals from renewable resources, such as lignocellulosic biomass, that can substitute for chemicals derived from fossil fuels. The bacterium Novosphingobium aromaticivorans is a promising microbial platform for producing commodity chemicals from lignocellulosic biomass because it can produce these from compounds in pretreated lignocellulosic biomass, which many industrial microbial catalysts cannot metabolize. Here, we show that N. aromaticivorans can be engineered to produce several valuable carotenoids. We also show that engineered N. aromaticivorans strains can produce these lipophilic chemicals concurrently with the extracellular commodity chemical 2-pyrone-4,6-dicarboxylic acid when grown in a complex liquor obtained from alkaline pretreated lignocellulosic biomass. Concurrent microbial production of valuable intra- and extracellular products can increase the economic value generated from the conversion of lignocellulosic biomass-derived compounds into commodity chemicals and facilitate the separation of water- and membrane-soluble products., Competing Interests: The authors declare no conflict of interest.

In order to address the problems of poor treatment effect of coal chemical wastewater (CCW) biochemical treatment system resulting in non-compliance with effluent standards and unstable operation, a combination regulation method of co-substrate metabolism and predominant flora enhancement was constructed, and the performance and mechanism of enhanced degradation of aromatics in CCW was also investigated in this study. The results showed that when the influent concentration of chemical oxygen demand (COD) and aromatics was less than 600 mg/L and 180 mg/L respectively, there was no significant effect of the combined regulation method on the enhanced treatment of aromatics, the removal rate of total organic carbon (TOC) in the system could all more than 73%; while when the influent concentration of COD increased to 800 mg/L and the aromatics concentration increased to more than 240 mg/L, the ordinary activated sludge system had collapsed. Compared with the regulation method of co-substrate metabolism alone, the combination regulation method increased the removal rate of TOC by 21%. The analysis of antioxidant enzyme activity showed that under the combination regulation method, the antioxidant enzyme activity of microorganisms was higher and their resistance to adverse environments was stronger. EPS and dehydrogenase analysis indicated that the combination regulation method was more conducive to microbial degradation of aromatics. Meanwhile, the analysis of microbial community structure showed that the aromatics degradation bacteria genera Rhodococcus, Luteococcus, etc. were enriched under the combination regulation method. The study provides a theoretical basis and technical guidance for solving the problems of unstable operation of CCW biochemical treatment systems and non-compliance with effluent standards., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2023. Published by Elsevier Ltd.)

Anthropogenic aromatics play a key role in photochemical pollution and pose a serious threat to human health. Current knowledge on source characteristics of aromatics in the urban region of the Tibetan Plateau (TP), the "Third Pole" and ecologically sensitive area, remains limited. In this study, an intensive observation of 17 aromatic hydrocarbons was conducted in Lhasa, the cultural and economic center of TP, during the second Tibetan Plateau Scientific Expedition and Research in summer 2020. The results showed that the average concentration of aromatics in Lhasa (7.6 ± 7.4 ppbv) was unexpectedly higher than those in megacities such as Beijing, Shanghai, and Guangzhou. Tripled concentrations and corresponding ozone formation potential during pollution episodes were recorded. Further source apportionment using positive matrix factorization revealed that solvent usage (60.0 %) was the dominant source, which may be due to the extremely low atmospheric pressure. Vehicle exhaust (15.4 %), industrial emissions (12.8 %), fuel evaporation (6.2 %), and burning emissions (5.7 %) were also important sources. The concentration weighted trajectory analysis revealed that the observed high levels of aromatics were mainly driven by local anthropogenic emissions, rather than the regional transport by the Indian summer monsoon. Long-term exposure to aromatics in Lhasa was assessed to pose carcinogenic risks to the population, with the risks of benzene and ethylbenzene 5 times the criteria. Our results suggest that, given the magnified emissions of aromatics in this extreme environment (low atmospheric pressure and strong solar radiation), the implementation of targeted pollution controls is urgently needed to mitigate the aromatic-related photochemical pollution and health threats in TP., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2023 Elsevier B.V. All rights reserved.)

Nitrogen-containing organic compounds (NOCs), a type of important reactive-nitrogen species, are abundant in organic aerosols in haze events observed in Northern China. However, due to the complex nature of NOCs, the sources, formation, and influencing factors are still ambiguous. Here, the molecular composition of organic matters (OMs) in hourly PM 2.5 samples collected during a haze event in Northern China was characterized using Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS). We found that CHON compounds (formulas containing C, H, O, and N atoms) dominated the OM fractions during the haze and showed high chemodiversity and transformability. Relying on the newly developed revised-workflow and oxidation-hydrolyzation knowledge for CHON compounds, 64% of the major aromatic CHON compounds (>80%) could be derived from the oxidization or hydrolyzation processes. Results from FT-ICR MS data analysis further showed that the aerosol liquid water (ALW)-involved aqueous-phase reactions are important for the molecular distribution of aromatic-CHON compounds besides the coal combustion, and the ALW-involved aromatic-CHON compound formation during daytime and nighttime was different. Our results improve the understanding of molecular composition, sources, and potential formation of CHON compounds, which can help to advance the understanding for the formation, evolution, and control of haze.

Diboriranides are the smallest conceivable monoanionic aromatic cycles, yet only limited examples have been reported and their reactivity and complexation behavior remain completely unexplored. We report a straightforward synthesis of the first peraryl diboriranide c-(DurB) 2 CPh - as its lithium salt in three steps via the corresponding non-classical diborirane from a readily available 1,2-dichlorodiborane(4) (Dur=2,3,5,6-tetramethylphenyl). With the preparation and complete characterization of representative complexes with tin, copper, gold and zinc, we demonstrate the strong preference of the diboriranide for σ-type coordination modes towards main group and transition metal centers under unperturbed retention of the three-membered B 2 C-ring's 2e - π-system., (© 2023 The Authors. Angewandte Chemie International Edition published by Wiley-VCH GmbH.)

Urinary mercapturic acids (MAs) are often used as biomarkers for monitoring human exposures to occupational and environmental xenobiotics. In this study, we developed an integrated library-guided analysis workflow using ultraperformance liquid chromatography-quadrupole time-of-flight mass spectrometry. This method includes expanded assignment criteria and a curated library of 220 MAs and addresses the shortcomings of previous untargeted approaches. We employed this workflow to profile MAs in the urine of 70 participants─40 nonsmokers and 30 smokers. We found approximately 500 MA candidates in each urine sample, and 116 MAs from 63 precursors were putatively annotated. These include 25 previously unreported MAs derived mostly from alkenals and hydroxyalkenals. Levels of 68 MAs were comparable in nonsmokers and smokers, 2 MAs were higher in nonsmokers, and 46 MAs were elevated in smokers. These included MAs of polycyclic aromatic hydrocarbons and hydroxyalkenals and those derived from toxicants present in cigarette smoke (e.g., acrolein, 1,3-butadiene, isoprene, acrylamide, benzene, and toluene). Our workflow allowed profiling of known and unreported MAs from endogenous and environmental sources, and the levels of several MAs were increased in smokers. Our method can also be expanded and applied to other exposure-wide association studies.

Aromatics are valuable bulk or fine chemicals with a myriad of important applications. Currently, their vast majority is produced from petroleum associated with many negative aspects. The bio-based synthesis of aromatics contributes to the much-required shift towards a sustainable economy. To this end, microbial whole-cell catalysis is a promising strategy allowing the valorization of abundant feedstocks derived from biomass to yield de novo-synthesized aromatics. Here, we engineered tyrosine-overproducing derivatives of the streamlined chassis strain Pseudomonas taiwanensis GRC3 for efficient and specific production of 4-coumarate and derived aromatics. This required pathway optimization to avoid the accumulation of tyrosine or trans-cinnamate as byproducts. Although application of tyrosine-specific ammonia-lyases prevented the formation of trans-cinnamate, they did not completely convert tyrosine to 4-coumarate, thereby displaying a significant bottleneck. The use of a fast but unspecific phenylalanine/tyrosine ammonia-lyase from Rhodosporidium toruloides (RtPAL) alleviated this bottleneck, but caused phenylalanine conversion to trans-cinnamate. This byproduct formation was greatly reduced through the reverse engineering of a point mutation in prephenate dehydratase domain-encoding pheA. This upstream pathway engineering enabled efficient 4-coumarate production with a specificity of >95% despite using an unspecific ammonia-lyase, without creating an auxotrophy. In shake flask batch cultivations, 4-coumarate yields of up to 21.5% (Cmol/Cmol) from glucose and 32.4% (Cmol/Cmol) from glycerol were achieved. Additionally, the product spectrum was diversified by extending the 4-coumarate biosynthetic pathway to enable the production of 4-vinylphenol, 4-hydroxyphenylacetate, and 4-hydroxybenzoate with yields of 32.0, 23.0, and 34.8% (Cmol/Cmol) from glycerol, respectively., Competing Interests: Declaration of competing interest The authors declare no competing interest., (Copyright © 2023 The Authors. Published by Elsevier Inc. All rights reserved.)

Zeolites, being acidic, act as the most promising catalytic materials for deoxygenating reactive oxygenated compounds produced during the pyrolysis of lignocellulosic biomass. Herein, two zeolites, HY and HZSM-5, with different Si/Al ratios, were employed to investigate the effect of zeolite structure on aromatic hydrocarbons (AHs) production during flash hydropyrolysis of cotton stalks (Temperature = 800 ˚C, H 2 pressure = 10 bar). Both the zeolites enhanced AHs production. However, the pore structure and pore size of HZSM-5 marked a pronounced effect on the reduction of oxygenated compounds. With an increase in Si/Al ratio, AHs area% was found to decrease owing to the decrease in acidity. Ni/zeolite catalysts were also investigated to look into the effect of metal loading on the catalytic properties of zeolites. Ni/zeolite catalysts enhanced the aromatic and aliphatic hydrocarbon production by further conversion of phenolics and other oxygenated compounds due to the promotion of direct deoxygenation, decarbonylation and decarboxylation reactions., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2023 Elsevier Ltd. All rights reserved.)

Lamiaceae is one of the largest botanical families, encompassing over 6000 species that include a variety of aromatic and medicinal spices. The current study is focused on three plants within this botanical family: basil ( Ocimum basilicum L.), thyme ( Thymus vulgaris L.), and summer savory ( Satureja hortensis L.). These three species contain primary and secondary metabolites such as phenolic and flavonoid compounds, fatty acids, antioxidants, and essential oils and have traditionally been used for flavoring, food preservation, and medicinal purposes. The goal of this study is to provide an overview of the nutraceutical, therapeutic, antioxidant, and antibacterial key features of these three aromatics to explore new breeding challenges and opportunities for varietal development. In this context, a literature search has been performed to describe the phytochemical profile of both primary and secondary metabolites and their pharmacological uses, as well as to further explore accession availability in the medicine industry and also to emphasize their bioactive roles in plant ecology and biotic and abiotic stress adaptability. The aim of this review is to explore future perspectives on the development of new, highly valuable basil, summer savory, and thyme cultivars. The findings of the current review emphasize the importance of identifying the key compounds and genes involved in stress resistance that can also provide valuable insights for further improvement of these important medicinal plants.

Py-GC/MS combines pyrolysis with analytical tools of gas chromatography (GC) and mass spectrometry (MS) and is a quick and highly effective method to analyse the volatiles generated from small amounts of feeds. The review focuses on using zeolites and other catalysts in the fast co-pyrolysis of various feedstocks, including biomass wastes (plants and animals) and municipal waste materials, to improve the yield of specific volatile products. The utilisation of zeolite catalysts, including HZSM-5 and nMFI, results in a synergistic reduction of oxygen and an increase in the hydrocarbon content of pyrolysis products. The literature works also indicate HZSM-5 produced the most bio-oil and had the least coke deposition among the zeolites tested. Other catalysts, such as metals and metal oxides, and feedstocks that act as catalysts (self-catalysis), such as red mud and oil shale, are also discussed in the review. Combining catalysts, such as metal oxides and HZSM-5, further improves the yields of aromatics during co-pyrolysis. The review highlights the need for further research on the kinetics of the processes, optimisation of feed-to-catalyst ratios, and stability of catalysts and products.

Lignin, the second largest component of biomass, is considered as an important alternative source of fossil reserves for the production of fuels and chemicals. Here, we developed a novel method to oxidatively degrade organosolv lignin into value-added four-carbon esters, particularly diethyl maleate (DEM), with the cooperative catalyst consisting of 1-(3-sulfobutyl) triethylammonium hydrogen sulfate ([BSTEA]HSO 4 ) and 1-butyl-3-methylimidazolium ferric chloride ([BMIM]Fe 2 Cl 7 ). Under optimized conditions (1.00 MPa initial O 2 pressure, 160 °C, 5 h), the lignin aromatic ring was effectively cleaved by oxidation to form DEM with a yield of 15.85% and a selectivity of 44.25% in the presence of the synergistic catalyst of [BMIM]Fe 2 Cl 7 -[BSMIM]HSO 4 (1/3, mol/mol). The structure and composition analysis of lignin residues and liquid products confirmed that the aromatic units in lignin were effectively and selectively oxidized. Furthermore, the catalytic oxidation of lignin model compounds was explored for obtaining a possible reaction pathway of oxidative cleavage of lignin aromatic units to DEM. This study provides a promising alternative method for the production of traditional petroleum-based chemicals.

Selective sorption of volatile aromatic compounds is a challenging issue for their total abatement. Despite the well-known affinity of palladium toward rich π systems, studies dedicated to volatile organic compound (VOC) capture with Pd(II)-based metal-organic frameworks (MOFs) are still very scarce. Intending to shed more light on this complex topic, this work compares the adsorption properties of two isostructural MOFs [Cu(2-pymo) 2 ] n and [Pd(2-pymo) 2 ] n and their selectivity for the sorption of linear, cyclic, or aromatic VOCs. The combination of both experimental and computational investigations highlights an increasing aromatic affinity over saturated hydrocarbons when palladium is chosen as a metal center ( n Benzene / n n -hexane = 1.8 at 0.5 p/p 0 ) in the MOF instead of copper ( n Benzene / n n -hexane = 0.7 at 0.5 p/p 0 ). Furthermore, [Pd(2-pymo) 2 ] n clearly exhibits preferential adsorption of benzene over toluene ( n Benzene / n Toluene = 1.7 at 0.5 p/p 0 ), due to the steric hindrance effects of the latter. The present results clearly underline the attractiveness of Pd-based MOFs for the design of selective aromatic adsorbents. Moreover, they also highlight the [Pd(2-pymo) 2 ] n MOF as a relevant candidate for the selective capture of benzene, by a synergistic combination of both charge interactions and steric hindrance effects.

Microplastics (MPs) are frequently detected in urban waters, which would pose a threat to human health through the food chain. Thus, efficient approaches to the elimination of MPs are urgently required. Pyrolysis is a powerful technique for the potential treatment of MPs. The online thermogravimetry-Fourier transform infrared reflection-Mass spectrometry (TG-FTIR-MS) is applied for tracking the pyrolysis process of representative polyethylene (PE) and polyvinyl chloride (PVC) MPs in urban waters, together with or without the FeAlO x catalyst. TG could quantitatively determine the decomposition behavior and kinetics of MPs while FTIR and MS spectra would be capable of characterizing the pyrolysis products. The results revealed that FeAlO x is an excellent carbon support, and the deposited carbon can be gasified to CO at higher pyrolysis temperatures. Moreover, more aromatic compounds were generated from the pyrolysis of PE MPs with the catalyzation of FeAlO x . Large quantities of benzene were also produced in the PVC MPs pyrolysis with or without FeAlO x . Also, FeAlO x largely decreased the concentrations of chlorine-containing compounds in the liquid products of PVC MPs pyrolysis. This study provides a efficient technique for the online observation of the MPs' catalytic pyrolysis process, which would guide future upcycling of MPs into value-added products., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2022 Elsevier B.V. All rights reserved.)

To investigate the formation of secondary organic aerosol (SOA) under current atmospheric conditions, we conducted a field observation of SOA precursors in the downwind region of the Yangtze River Delta (YRD) in winter 2019 using a variety of offline and online instruments. During the entire observation period, the averaged fine particulate SOA was 7.9 ± 2.3 μg m -3 , with precursor concentrations of 31 ± 11 ppbv for the measured volatile organic compounds (VOCs) and 16 ± 12 ppbv for NOx. Compared to those on the clean days, SOA on the haze days increased by a factor of 1.6, while the VOC and NOx increased by a factor of 1.3 and 2.0, respectively. Aerosol liquid water content (ALWC) and oxygenated VOCs (OVOCs, including acetaldehyde, formic acid, acetone, acetic acid, methyl ethyl ketone, and methylglyoxal) relationships suggested that the gasSOA and aqSOA occurred simultaneously on Chongming Island in winter. The gasSOA was primarily formed by the oxidation of aromatics and NOx at low RH (RH < 80%) conditions. In contrast, the aqSOA was formed under higher RH (RH > 80%) conditions via a combination of daytime photochemical aqueous phase processes of water-soluble OVOCs and nocturnal dark aqueous phase processes of primary emissions from biomass. The inversed higher mass ratio of NACs to (benzene + toluene) and nitrogen oxidation ratio (NOR) in the daytime during the gasSOA-dominated haze periods indicated that gasSOA could be transformed to aqSOA at high NOx levels. Our results also suggested the importance of NOx and VOC reduction measures in directly mitigating gasSOA and indirectly mitigating aqSOA during winter haze pollution., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2022 Elsevier Ltd. All rights reserved.)

Background: Lignocellulosic resources are promising feedstocks for the manufacture of bio-based products and bioenergy. However, the inherent recalcitrance of biomass to conversion into simple sugars currently hinders the deployment of advanced bioproducts at large scale. Lignin is a primary contributor to biomass recalcitrance as it protects cell wall polysaccharides from degradation and can inhibit hydrolytic enzymes via non-productive adsorption. Several engineering strategies have been designed to reduce lignin or modify its monomeric composition. For example, expression of bacterial 3-dehydroshikimate dehydratase (QsuB) in poplar trees resulted in a reduction in lignin due to redirection of metabolic flux toward 3,4-dihydroxybenzoate at the expense of lignin. This reduction was accompanied with remarkable changes in the pools of aromatic compounds that accumulate in the biomass., Results: The impact of these modifications on downstream biomass deconstruction and conversion into advanced bioproducts was evaluated in the current study. Using ionic liquid pretreatment followed by enzymatic saccharification, biomass from engineered trees released more glucose and xylose compared to wild-type control trees under optimum conditions. Fermentation of the resulting hydrolysates using Rhodosporidium toruloides strains engineered to produce α-bisabolene, epi-isozizaene, and fatty alcohols showed no negative impact on cell growth and yielded higher titers of bioproducts (as much as + 58%) in the case of QsuB transgenics trees., Conclusion: Our data show that low-recalcitrant poplar biomass obtained with the QsuB technology has the potential to improve the production of advanced bioproducts., (© 2022. The Author(s).)

This work comprehensively investigated the constituents, sources, and associated health risks of ambient volatile organic compounds (VOCs) sampled during the autumn of 2020 in urban Nanjing, a megacity in the densely populated Yangtze River Delta region in China. The total VOC (TVOC, sum of 108 species) concentration was determined to be 29.04 ± 14.89 ppb, and it was consisted of alkanes (36.9%), oxygenated VOCs (19.9%), halogens (19.1%), aromatics (9.9%), alkenes (8.9%), alkynes (4.9%), and others (0.4%). The mean TVOC/NO x (ppbC/ppbv) ratio was only 3.32, indicating the ozone control is overall VOC-limited. In terms of the ozone formation potential (OFP), however, the largest contributor became aromatics (41.9%), followed by alkenes (27.6%), and alkanes (16.9%); aromatics were also the dominant species in secondary organic aerosol (SOA) formation, indicative of the critical importance of aromatics reduction to the coordinated control of ozone and fine particulate matter (PM 2.5 ). Mass ratios of ethylbenzene/xylene (E/X), isopentane/n--pentane (I/N), and toluene/benzene (T/B) ratios all pointed to the significant influence of traffic on VOCs. Positive matrix factorization (PMF) revealed five sources showing that traffic was the largest contributor (29.2%), particularly in the morning. A biogenic source, however, became the most important source in the afternoon (31.3%). The calculated noncarcinogenic risk (NCR) and lifetime carcinogenic risk (LCR) of the VOCs were low, but four species, acrolein, benzene, 1,2-dichloroethane, and 1,2-dibromoethane, were found to possess risks exceeding the thresholds. Furthermore, we conducted a multilinear regression to apportion the health risks to the PMF-resolved sources. Results show that the biogenic source instead of traffic became the most prominent contributor to the TVOC NCR and its contribution in the afternoon even outpaced the sum of all other sources. In summary, our analysis reveals the priority of controls of aromatics and traffic/industrial emissions to the efficient coreduction of O 3 and PM 2.5 ; our analysis also underscores that biogenic emissions should be paid special attention if considering the direct health risks of VOCs.

As an alternative route for aromatics and hydrogen production, methane dehydroaromatization (MDA) is of significant academic and industrial interest due to the abundance of natural gas resources and the intensive demand for aromatics and CO x -free hydrogen. In the present work, a simulation study on MDA in membrane reactors (MRs) was performed with the aim of co-producing aromatics and CO x -free hydrogen with a highly improved efficiency. The effects of various parameters, including catalytic activity, membrane flux and selectivity, as well as the operating conditions on the MR performance were discussed with respect to methane conversion, hydrogen yield, and hydrogen purity. The results show that catalytic activity and membrane flux and selectivity have significant impacts on CH 4 conversion and H 2 yield, whereas H 2 purity is mainly dominated by membrane selectivity. A highly improved MDA is confirmed to be feasible at a relatively low temperature and a high feed pressure because of the hydrogen extraction effect. To further improve MDA in MRs by intensifying H 2 extraction, a simple configuration combining a fixed-bed reactor (FBR) and an MR together is proposed for MDA, which demonstrates good potential for the high-efficiency co-production of aromatics and CO x -free hydrogen.

With the rapid development of industrial society and humankind's prosperity, the growing demands of global energy, mainly based on the combustion of hydrocarbon fossil fuels, has become one of the most severe challenges all over the world. It is estimated that fossil fuel consumption continues to grow with an annual increase rate of 1.3%, which has seriously affected the natural environment through the emission of greenhouse gases, most notably carbon dioxide (CO 2 ). Given these recognized environmental concerns, it is imperative to develop clean technologies for converting captured CO 2 to high-valued chemicals, one of which is value-added hydrocarbons. In this article, environmental effects due to CO 2 emission are discussed and various routes for CO 2 hydrogenation to hydrocarbons including light olefins, fuel oils (gasoline and jet fuel), and aromatics are comprehensively elaborated. Our emphasis is on catalyst development. In addition, we present an outlook that summarizes the research challenges and opportunities associated with the hydrogenation of CO 2 to hydrocarbon products., (Copyright © 2022 Cui, Liu, Yao, Edwards, Xiao and Cao.)

The use of lignin to produce Benzene, Toluene and Xylene (BTX) is a promising pathway to strength the economic case, over the production of advanced bio-fuels alone. In this work, Ce, Na, Pd and Fe supported on zirconium oxide were evaluated for the ex-situ hydropyrolysis (HyPy)/hydrodeoxygenation (HDO) of Etek lignin under mild conditions (600 °C, 1 atmosphere) towards the production of BTX. Fe/ZrO 2 was able to selectively produce BTX (67 area%) and cycloalkenes (13.5 area%) and strongly deoxygenate the HyPy oil to about 5 wt% oxygen content, resulting in an oil with a carbon distribution of 85.5 % in C 5 -C 10 hydrocarbons. The high selectivity of Fe/ZrO 2 was related to the iron oxophilicity, the strong reduction potential of zero-valent iron, the good dispersion of Fe nanoparticles on the support and the presence of mesopores and acid sites, which enhanced the interactions between the reacting species and the catalyst surface., (Copyright © 2022 The Author(s). Published by Elsevier Ltd.. All rights reserved.)

Automotive painting plants are important emission sources of volatile organic compounds (VOCs) that contribute significantly to ground-level ozone (O₃) pollution in atmosphere. Here, we investigated process-specified emission characteristics of VOCs, without or with advanced adsorption/incineration after-treatments, from an ultra-low-emission (ULE) waterborne painting process in a modernized automotive plant. Overall, more than 80 VOCs species were identified and sorted into seven main categories. In the stack emissions without after-treatments, oxygenated VOCs (alcohols, esters, ketones, ethers, etc.) were found to be the most abundant components (48.8%), followed by aromatic (30.9%), alkanes (16.9%) and alkenes (1.2%). Among the different VOCs species discharged to atmosphere (i.e. after adsorption/incineration after-treatments), aromatics demonstrated a predominant contribution (by 60.6%) to the total O₃ formation potentials (OFPs) despite their relatively lower abundance. Trimethylbenzene was identified to have the highest OFPs, and thus should be controlled with peculiar priority. As compared to traditional organic solvent-based painting process, the ULE waterborne process implemented in the target plant allows to reduce the OFPs from 10.7 mg m -3 to 3 mg m -3 (or by 72%). Additional monitoring by unmanned aerial vehicle (over more than 3000 sampling points in the plant) confirmed that the instantaneous concentrations of fugitive VOCs were well below the regulated limit value during typical working and non-working days. These findings may provide important reference for reduction of VOCs emissions and O 3 pollution from automotive painting processes., (Copyright © 2022 Elsevier Ltd. All rights reserved.)

2-Phenylethanol (2-PE) is a rose-scented aromatic compound, with broad application in cosmetic, pharmaceutical, food and beverage industries. Many plants naturally synthesize 2-PE via Shikimate Pathway, but its extraction is expensive and low-yielding. Consequently, most 2-PE derives from chemical synthesis, which employs petroleum as feedstock and generates unwanted by products and health issues. The need for "green" processes and the increasing public demand for natural products are pushing biotechnological production systems as promising alternatives. So far, several microorganisms have been investigated and engineered for 2-PE biosynthesis, but a few studies have focused on autotrophic microorganisms. Among them, the prokaryotic cyanobacteria can represent ideal microbial factories thanks to their ability to photosynthetically convert CO 2 into valuable compounds, their minimal nutritional requirements, high photosynthetic rate and the availability of genetic and bioinformatics tools. An engineered strain of Synechococcus elongatus PCC 7942 for 2-PE production, i.e., p120, was previously published elsewhere. The strain p120 expresses four heterologous genes for the complete 2-PE synthesis pathway. Here, we developed a combined approach of metabolite doping and metabolic engineering to improve the 2-PE production kinetics of the Synechococcus elongatus PCC 7942 p120 strain. Firstly, the growth and 2-PE productivity performances of the p120 recombinant strain were analyzed to highlight potential metabolic constraints. By implementing a BG11 medium doped with L-phenylalanine, we covered the metabolic burden to which the p120 strain is strongly subjected, when the 2-PE pathway expression is induced. Additionally, we further boosted the carbon flow into the Shikimate Pathway by overexpressing the native Shikimate Kinase in the Synechococcus elongatus PCC 7942 p120 strain (i.e., 2PE&#95; aroK ). The combination of these different approaches led to a 2-PE yield of 300 mg/gDW and a maximum 2-PE titer of 285 mg/L, 2.4-fold higher than that reported in literature for the p120 recombinant strain and, to our knowledge, the highest recorded for photosynthetic microorganisms, in photoautotrophic growth condition. Finally, this work provides the basis for further optimization of the process aimed at increasing 2-PE productivity and concentration, and could offer new insights about the use of cyanobacteria as appealing microbial cell factories for the synthesis of aromatic compounds., Competing Interests: The authors declare that the research was conducted in the absence of any commercial or financial relationships that could be construed as a potential conflict of interest., (Copyright © 2022 Usai, Cordara, Re, Polli, Mannino, Bertea, Fino, Pirri and Menin.)

To investigate the characteristics and sources of atmospheric volatile organic compounds (VOCs) in a typical industrial zone in Dongguan, 56 VOCs species were continuously measured in Houjie Town of Dongguan in summer of 2020. In addition, mass concentrations of O 3 , NO x , and CO and meteorological data were synchronously collected. Then, characteristics of total VOCs and major species, the contributions of major VOCs species to ozone formation potential (OFP), and source apportionment of VOCs under the different ozone concentrations were discussed. The mean mixing ratio of VOCs was 53.1×10 -9 including aromatics (24.7×10 -9 ), alkanes (23.7×10 -9 ), alkenes (3.9×10 -9 ), and alkynes (0.7×10 -9 ). The mean mixing ratios of aromatics, alkanes, alkenes, and alkynes increased approximately 10%, 43%, 38%, and 98% during the period of ozone pollution, respectively, compared with those during the period of non-ozone pollution. Aromatics contributed the most to OFP during the periods of both ozone pollution and non-ozone pollution, followed by alkanes, alkenes, and alkynes. Solvent sources, liquefied petroleum gas (LPG) leakage, fossil fuel combustion, and hydrocarbon volatilization were resolved using the PMF model, which accounted for 60%±20%, 16%±11%, 15%±11%, and 9%±6% of total VOCs, respectively. During the period of ozone pollution, the contribution of solvent sources to the total VOCs decreased to 44%, whereas that of LPG leakage and hydrocarbon volatilization increased to 21% and 16%, respectively.

In this work, Cu-SrO bimetallic catalyst was synthesised and examined for catalytic co-pyrolysis of ironbark (IB) and waste cooking oil (WCO) using Py-GC/MS. The effect of catalyst supports (ZSM-5, Y-zeolite, activated carbon, Al 2 O 3 , and ZrO 2 ) on aromatic hydrocarbons yield was studied. The effect of catalyst support on the selectivity of gasoline (C8-C14), diesel (C15-C17), and heavy oil (>C20) components of bio-oil were studied. Non-catalytic co-pyrolysis of IB and WCO produced a heavy oil component of 58.7% (>C20). SrO initiated a ketonization reaction that converted carboxylic acids into new C-C bonds. The addition of Cu effectively promoted secondary cracking and aromatization reactions enhancing the hydrocarbon yield. Cu-SrO/ZSM-5 and Cu-SrO/Y-zeolite produced low acid content of 4.43% and 12.5%, respectively. Overall, the bimetallic catalyst Cu-SrO/ZSM-5 significantly increased the amount of C8-C14 compounds to 87.28% and reduced compounds over C20 to 1.19%., (Copyright © 2022 Elsevier Ltd. All rights reserved.)

This study aims to propose a method for upgrading biomass pyrolysis products based on the combination of sodium persulfate pretreatment and fast catalytic pyrolysis. Combined with the analysis of components and thermogravimetric analysis, the result showed that after pretreatment the biomass structure was gradually depolymerized, the contents of lignin, the reaction of activation energy and the crystallinity of cellulose decreased. Due to the destructive effect of persulfate radicals, in fast pyrolysis, the relative contents of acids and oxygen-containing substances decreased, and the relative content of phenols can significantly increase to 19.20%. The yield of aromatic hydrocarbons and total hydrocarbons had a high value under the catalytic pyrolysis in the best performance which amount of yield reached 28.66% and 33.72%, respectively. Sodium persulfate pretreatment was beneficial in the production of hydrocarbon-rich bio-oils and high-value chemicals since the radicals can effectively depolymerize lignin which promoted the process of pyrolysis., (Copyright © 2022 Elsevier Ltd. All rights reserved.)

Catalytic pyrolysis is a promising chemical recycling technology to supplement mechanical recycling since plastics can be broken down into monomers or converted to the required fuels and chemicals. In this study, a microwave (MW) -responsive SiC foam@zeoltie core-shell structured catalyst was proposed for the catalytic pyrolysis of polyolefins. Under microwave irradiation, the SiC foam core works as both microwave adsorber and catalyst support, thus concentrating the generated heat energy on the ZSM-5 zeolite shell, where the catalytic reaction takes place. SiC foam with an open cellular structure can also improve the global transport of mass and heat during plastics pyrolysis. In this work, the effects of the SiO 2 /Al 2 O 3 ratio and alkaline treatment of ZSM-5 zeolite coated SiC foam under MW irradiation on the variations in product distribution from low-density polyethylene (LDPE) pyrolysis were investigated at 450 °C. The results indicated that the appropriate acidity and pore structure were crucial to upgrading gas and liquid products. Particularly, the creation of a mesoporous structure in ZSM-5 zeolite via alkaline treatment could improve the diffusion of large molecules and products, thus significantly increasing the selectivity of high-valued light olefins and aromatics while inhibiting the formation of unwanted alkanes, which are expected in the chemical industry. Concretely, the concentration of olefins in gas increased to 51.0 vol% for ZSM-5(50)-0.25AT, and 65.6 vol% for ZSM-5 (50)-0.50AT, compared with 45.2 vol% for the parent ZSM-5(50). The relative concentration of aromatics in liquid decreased from 96.6% for ZSM-5(50) to 75.9% for ZSM-5(50)-0.25AT, and 71.1% for ZSM-5(50)-0.50AT. Given the respective yield of gas and liquid, the total selectivity of C2-C4 olefins and aromatics for mesoporous ZSM-5 zeolites could reach 58.6-64.9% during LDPE pyrolysis, which were higher than that for the parent ZSM-5 zeolite., (Copyright © 2022 Elsevier Ltd. All rights reserved.)

In this study, the adsorption of benzoic acid and phenols in the aqueous phase by MOF-Cu adsorbent was investigated. A high-performance liquid chromatography (HPLC) device was used to analyze the concentration of contaminants in the solution. Three isotherms, Freundlich, Langmuir, and Temkin were performed for adsorption of Benzoic Acid (BA) and Phenol contaminants. Correlation factor for adsorption isotherms were fitted into Langmuir aqueous BA and Phenol would be 99.89 and 99.98%, respectively. The equilibrium adsorption capacity MOF-Cu of BA and Phenol is 636.73 and 524.42 mg/g, respectively. In this study, high contaminant adsorption with π-π interaction and hydrogen bonding leads to the high capacity of MOFCu. In addition, the increase in adsorption capacity of benzoic acid is due to the electronegative property of oxygen in the carbonyl group and the similarity of the carboxylic acid functional group with the adsorbent. The result shows, that at initial time adsorption, has been a non-linear trend. In addition, the first-order kinetic model is not a suitable option for fitting the experimental data of adsorption kinetics and the adsorption kinetics of BA and Phenol is very well compatible with the semi-second order with the correlation Factor being 99.7 and 99.78, respectively. Also, the equilibrium adsorption capacity in pseudo-second order kinetic for BA and Phenol is 613.5 and 523.56 mg/g respectively., (Copyright © 2022 Elsevier B.V. All rights reserved.)

Hierarchical utilization of substrate by microbes (utilization of simple carbon sources prior to complex ones) poses a major limitation to the efficient remediation of aromatic pollutants. Aromatic compounds, being complex and reduced in nature, appear to be a deferred choice as the carbon source in the presence of a plethora of simple organic compounds in the environment. The soil bacterium Pseudomonas bharatica CSV86 T displays a unique carbon source utilization hierarchy. It preferentially utilizes aromatics over glucose and co-metabolizes them with succinate or pyruvate (Basu et al ., 2006, Applied and Environmental Microbiology , 72 : 22226-2230). In the present study, the substrate utilization hierarchy for strain CSV86 T was tested for additional simple carbon sources such as glycerol, acetate, and tri-carboxylic acid (TCA) cycle intermediates like α-ketoglutarate and fumarate. When grown on a mixture of aromatics (benzoate or naphthalene) plus glycerol, the strain displayed a diauxic growth profile with significantly high activity of aromatic utilization enzymes (catechol 1,2- or 2,3-dioxygenase, respectively) in the first-log phase. This suggests utilization of aromatics in the first-log phase followed by glycerol in the second-log phase. On a mixture of an aromatic plus organic acid (acetate, α-ketoglutarate or fumarate), the strain displayed a monoauxic growth profile, indicating co-metabolism. Interestingly, the presence of glycerol, acetate, α-ketoglutarate or fumarate does not repress metabolism/utilization of the aromatic. Thus, the substrate utilization hierarchy of strain CSV86 T is aromatics=organic acids>glucose/glycerol, which is unique as compared to other Pseudomonas species, where degradation of aromatics is repressed by glycerol, glucose, acetate or organic acids, including TCA cycle intermediates. This novel substrate utilization hierarchy appears to be a global metabolic phenomenon in strain CSV86 T , thus implying it to be an ideal host for metabolic engineering as well as for its potential application in bioremediation.

5-hydroxymethylfurfural (HMF) is one of the most valuable biomass platform molecules, enabling the construction of a plethora of high value-added furanic compounds. In particular, in the last decade, HMF has been considered as a starting material for designing biobased surfactants, not only because of its renewability and carbon footprint, but also because of its enhanced biodegradability. This Review presents recent examples of the different approaches to link the hydrophilic and lipophilic moieties into the hydrophobic furan (and tetrahydrofuran) ring, giving a variety of biobased surfactants that have been classified here according to the charge of the head polar group. Moreover, strategies for the synthesis of different non-furanic structures surfactant molecules (such as levulinic acid, cyclopentanols, and aromatics) derived from HMF are described. The new HMF-based amphiphilic molecules presented here cover a wide range of hydrophilic-lipophilic balance values and have suitable surfactant properties such as surface tension activity and critical micelle concentration, to be an important alternative for the replacement of non-sustainable surfactants., (© 2022 The Authors. ChemSusChem published by Wiley-VCH GmbH.)

Energy shortage and environmental pollution have attracted long-term attention. In this study, CaO were prepared from waste eggshell (EGC), preserved egg shell (PEC), clam shell (CLC) and crab shell (CRC), which were then compared with commercial CaO (CMC) to catalyze microwave-assisted pyrolysis of waste cooking oil (WCO) for enrichment of aromatics in bio-oil. The characterization results indicated that EGC and CLC contained 95.54% and 95.61% CaO respectively, which were higher than that of CMC (95.11%), and the pore properties of EGC were the best. In addition, the effects of CaO type and catalytic mode on pyrolysis were studied. In CaO catalytic pyrolysis, CMC and CLC in-situ catalysis produced more aromatics than ex-situ catalysis, and PEC and CRC were more conducive to aromatics formation in ex-situ condition. EGC was conducive to produce benzene, toluene and xylene (BTX) both in in-situ (19.04%) and ex-situ (20.76%) catalytic pyrolysis. In CaO/HZSM-5 catalysis, the optimal dual catalytic mode for generating monocyclic aromatic hydrocarbons (MAHs) was Mode A (CaO separated from HZSM-5 for ex-situ catalysis), and EGC/HZSM-5 performed well in benzene, toluene and xylene (BTX) production., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2022 Elsevier B.V. All rights reserved.)

Catalytic fast pyrolysis of low sulfonated Kraft lignin was performed under different atmospheric environments such as N 2 , CH 4, and the gas derived from CH 4 decomposition (CH 4 -D). The use of Zn- or Mo-loaded HZSM-5 as catalyst led to a higher pyrolytic oil yield compared to parent HZSM-5 in CH 4 and CH 4 -D atmospheres. The yields of benzene, toluene, and xylenes were increased by the synergistic effects from metal loading, higher H/C eff ratio, higher acidity, and CH 4 activation. The enhanced CH 4 activation via metal loading resulted in higher methylation of alkyl moieties and 33% increase in the total yield of benzene, toluene, and xylenes in comparison to parent HZSM-5. A higher H/C eff ratio of 6 via CH 4 decomposition led to the formation of a hydro-pyrolysis environment. Moreover, the CH 4 -D environment showed H 2 /CH 4 ratio of 0.36 in the product gas which warranted the presence of more H 2 under the CH 4 -D pyrolysis environment., (Copyright © 2022 Elsevier Ltd. All rights reserved.)

The ability to degrade exogenous compounds is acquired by adaptive processes of microorganisms when they are exposed to compounds that are foreign to their existing enzyme systems. Previously, we reported that simultaneous point mutations and mobile genetic elements cause the evolution and optimization of the degradation systems for aromatic compounds. In the present study, we propose another element with this role-tandem repeats. The novel metagenomic tandem repeat (MTR) sequence T(G/A)ACATG(A/C)T was identified in the 5'-untranslated regions of catechol 2,3-dioxygenase (C23O)-encoding genes by metagenomic analysis. Recombinant Escherichia coli carrying a C23O gene with various numbers of MTRs exhibited increased C23O protein expression and enzyme activity compared with cells expressing the C23O gene without MTRs. Real-time reverse transcription PCR showed that changes in the numbers of MTRs affected the levels of detectable C23O mRNA in the E. coli host. Furthermore, the mRNAs transcribed from C23O genes containing various numbers of MTRs had longer half-lives than those transcribed from a C23O gene without MTRs. Thus, MTRs would affect the translation efficiency of the gene expression system. MTRs may change the expression levels of their downstream genes for adaptation to a fluctuating environment., (© The Author(s) 2022. Published by Oxford University Press on behalf of FEMS.)