Aromatic

In 1,1,1,3,3,3-hexafluoroisopropyl alcohol (HFIP), gem-bis(triflyl)cyclobutenes, which can be prepared by the (2+2) cycloaddition reaction of Tf2C=CH2 with alkynes, underwent desulfination to generate the corresponding cyclobutenyl cation. This unique reactivity was successfully applied to the Friedel-Crafts type cyclobutenylation reaction of several (hetero)aromatic compounds.

We report, for the first time, a new synthetic strategy for the preparation of crystalline two-dimensional olefin-linked covalent organic frameworks (COFs) based on aldol condensation between benzodifurandione and aromatic aldehydes. Olefin-linked COFs can be facilely crystallized through either a pyridine-promoted solvothermal process or a benzoic anhydride-mediated organic flux synthesis. The resultant COF leaf with high in-plane π-conjugation exhibits efficient visible-light-driven photoreduction of carbon dioxide (CO2 ) with water (H2 O) in the absence of any photosensitizer, sacrificial agents, or cocatalysts...

Pauling and Corey expected that a racemic mixture would result in a rippled β-sheet, however, it has been known from experiments that the racemic mixtures of triphenylalanine lead to a herringbone structure. Because of the theoretical limitations concerning crystal structures such as rippled β-sheet, it is inevitable to understand how the interplay of the amino acids prefers a specific structural motif. In this paper we use molecular dynamics to understand the sequence- and enantiomer-dependent structures by comparisons between rippled β-sheet and pleated β-sheet, solvated and anhydrous rippled β-sheet, and rippled β-sheet and the herringbone structure, based on thermodynamics and structures at the atomic level...

Understanding charge transfer processes is essential to estimate the performance of organic photovoltaic technologies. Although experimental production is on the rise, predictability strongly relies on theoretical modeling, which is limited to the size of semiconductors. As a computationally favorable approach, we benchmarked the long-range corrected (LC) time-dependent (TD) formulation of the semi-empirical density functional-based tight-binding method (DFTB) for three polycyclic aromatic hydrocarbons (PAHs) and studied the DTP-IC-4Ph molecule, a PAH-based non-fullerene electron acceptor (NFA) with an A-D-A backbone structure...

The C-H bond activation catalyzed by a manganese(I) complex has achieved significant development but is limited to C(sp2 )-H bonds. In this work, an efficient manganese(I)-catalyzed direct nucleophilic addition reaction of C(sp3 )-H bonds to aromatic aldehydes has been developed. This is the first example of manganese(I)-catalyzed C(sp3 )-H bond transformation. A manganacycle complex was isolated and proved to be the key active intermediate in the catalytic cycle.

The current study placed an intense emphasis on the excess discharge of agro-based industrial effluent and the use of plant extract antimicrobials to inhibit the growth of pathogens in crop plants. An effluent (treated and untreated) from the marigold flower processing industry has been identified for the presence of volatile and semi-volatile organic compounds, and a total of 18 in treated effluent and 23 in untreated effluent were found using gas chromatography-mass spectrometry. A total of 13 classes were identified, which include carboxylic acid, phenols, esters, alkanes, alkenes, alcohols, cyanide, heterocyclic, flavonoids, aldehydes, polycyclic aromatic, cycloalkanes, and cycloalkenes...

The catalytic coconversion of glycerol and toluene (93/7 wt %) over a technical H-ZSM-5/Al2 O3 (60-40 wt %) catalyst was studied, aiming for enhanced production of biobased benzene, toluene, and xylenes (bio-BTX). When using glycerol/toluene cofeed with a mass ratio of 93/7 wt %, a peak BTX carbon yield of 29.7 ± 1.1 C.% (at time on stream (TOS) of 1.5-2.5 h), and an overall BTX carbon yield of 28.7 C.% (during TOS of 8.5 h) were obtained, which are considerably higher than those (19.1 ± 0.4 C.% and 11...

This work sheds new light on the stereoselective synthesis of chiral macrocycles containing twisted aromatic units, valuable π-conjugated materials for recognition, sensing, and optoelectronics. For the first time, we use the Curtin-Hammett principle to investigate a chiral macrocyclisation reaction, revealing the potential for supramolecular π-π interactions to direct the outcome of a dynamic kinetic resolution, favouring the opposite macrocyclic product to that expected under reversible, thermodynamically controlled conditions...

Tetrapyridyl-functionalized phosphinines were prepared and structurally characterized. The donor-functionalized aromatic phosphorus heterocycles react highly selectively and even reversibly with water. Calculations reveal P,N-cooperativity for this process, with the flanking pyridyl groups serving to kinetically enhance the formal oxidative addition process of H2 O to the low-coordinate phosphorus atom via H-bonding. Subsequent tautomerization forms 1,2-dihydrophosphinine derivatives, which can be quantitatively converted back to the phosphinine by applying vacuum, even at room temperature...

The synthesis of BN-containing molecules, which have an interesting isosteric relationship to their parent all-C cores, has drawn a great deal of attention as an avenue to alter and tune molecular function. Nevertheless, many cores with embedded BN are still hard to synthesize, and thus, further effort is required in this direction. Herein, we present an integrated approach to BN-containing polycycles rooted in an exceptionally clean B-N condensation of amines with a tri-allylborane. Having released propene as the only byproduct, the resulting BN precursors are seamlessly telescoped into BN-containing polycyclic cores via a set of additional methodologies, either developed here ad-hoc or applied for the first time for the synthesis of BN-cycles...

Di- tert -butyldiphosphatetrahedrane ( t BuCP)2 (1) is a mixed carbon- and phosphorus-based tetrahedral molecule, isolobal to white phosphorus (P4 ). However, despite the fundamental significance and well-explored reactivity of the latter molecule, the precise structure of the free ( t BuCP)2 molecule (1) and a detailed analysis of its electronic properties have remained elusive. Here, single-crystal X-ray structure determination of 1 at low temperature confirms the tetrahedral structure. Furthermore, quantum chemical calculations confirm that 1 is isolobal to P4 and shows a strong largely isotropic diamagnetic response in the magnetic field and thus pronounced spherical aromaticity...

BACKGROUND: Mouthwashes play a pivotal role in oral care, and their efficacy has been explored extensively across various dimensions. As a contribution to the development of novel oral care products, this study aims to investigate the psychophysiological effects of aromatic mouthwashes during the resilience period from a short-term cognitive stressor utilizing biological signals and subjective evaluations. METHODS: A within-participant experimental design with 22 healthy females was conducted with four mouthwashes; peppermint (Mint), peppermint + bergamot (MB), peppermint + sweet orange (MO), and peppermint + lavender (ML), and water as the control (Ctl), after a 20-min calculation task...

While plastic water bottles are known to potentially release various volatile organic compounds (VOCs) when exposed to light, existing knowledge in this field remains limited. In this study, we systematically examined the composition, yield, and toxicity of VOCs released from six plastic containers obtained from different continents under UV-A and solar irradiation. After light exposure, all containers released VOCs, including alkanes, alkenes, alcohols, aldehydes, carboxylic acids, aromatics, etc. The 1#, 3#, 4#, 5#, and 6# containers exhibited 35, 32, 19, 24 and 37 species of VOCs, respectively...

Conjugated polymers with tailorable composition and microarchitecture are propitious for modulating catalytic properties and deciphering inherent structure-performance relationships. Herein, we report a facile linker engineering strategy to manipulate the electronic states of metallophthalocyanine conjugated polymers and uncover the vital role of organic linkers in facilitating electrocatalytic oxygen reduction reaction (ORR). Specifically, a set of cobalt phthalocyanine conjugated polymers (CoPc-CPs) wrapped onto carbon nanotubes (denoted CNTs@CoPc-CPs) are judiciously crafted via in situ assembling square-planar cobalt tetraaminophthalocyanine (CoPc(NH2)4) with different linear aromatic dialdehyde-based organic linkers in the presence of CNTs...

Atmospheric particulate matter (PM) has been related to numerous adverse health effects in humans. Nowadays, it is believed that one of the possible mechanisms of toxicity could be the oxidative stress, which involves the development of reactive oxygen species (ROS). Different assays have been proposed to characterize oxidative stress, such as dithiothreitol (DTT) and ascorbic acid (AA) acellular assays (OPDTT and OPAA ), as a metric more relevant than PM mass measurement for PM toxicity. This study evaluates the OP of the bioaccessible fraction of 65 PM10 samples collected at an Atlantic Coastal European urban site using DTT and AA assays...

Singlet oxygen (1O2) is an essential reactive species responsible for selective oxidation of organic matter, especially in Fenton-like processes. However, due to the great limitations in synthesizing catalysts with well-defined active sites, the controllable production and practical application of 1O2 remain challenging. Herein, guided by theoretical simulations, a series of boron nitride-based single-atom catalysts (BvBN/M, M = Co, Fe, Cu, Ni and Mn) were synthesized to regulate 1O2 generation by activating peroxymonosulfate (PMS)...

Microplastics (MPs) and persistent pollutants (POPs) are new pollutants that are extensively studied worldwide. To fill the gaps that the degradation processes and mechanisms of polycyclic aromatic hydrocarbons (PAHs) on the surface of most MPs are still unclear, the photochemical transformation of benzo(a)anthracene (BaA) on polyvinyl chloride (PVC) MPs and polystyrene (PS) MPs in water were investigated and compared. The photolysis of BaA on the surface of PS in water proceeded easier than that on PVC within the 48 h irradiation period, with the pseudo-first-order rate constant of 0...

Halogenated aromatic pollutants (HAPs) including polychlorinated dibenzo-p-dioxins/furans (PCDD/Fs), polychlorinated biphenyls (PCBs), polybrominated dibenzo-p-dioxins/furans (PBDD/Fs), and polybrominated diphenyl ethers (PBDEs) exhibit diverse toxicities and bio-accumulation in animals, thereby imposing risks on human via animal-derived food (ADF) consumption. Here we examined these HAPs in routine ADFs from South China and observed that PBDEs and PCBs showed statistically higher concentrations than PCDD/Fs and PBDD/Fs...

The dried fruit of Amomum villosum is an important spice and medicinal plant that has received great attention in recent years due to its high content of bioactive components and its potential for food additives and drug development. However, the stems and leaves of A. villosum are usually disposed of as waste. Based on the study of the fruits of A. villosum, we also systematically studied its stems and leaves. Fourteen aromatic compounds (1-14) were isolated and identified from A. villosum, including five new compounds (1-5) and nine known compounds (6-14)...

Pyrolysis can effectively convert waste tires into high-value products. However, the sulfur-containing compounds in pyrolysis oil and gas would significantly reduce the environmental and economic feasibility of this technology. Here, the desulfurization and upgrade of waste tire pyrolysis oil and gas were performed by adding different metal oxides (Fe2 O3 , CuO, and CaO). Results showed that Fe2 O3 exhibited the highest removal efficiency of 87.7 % for the sulfur-containing gas at 600 °C with an outstanding removal efficiency of 99...