Benzene Precursors Research Articles

Synthesis and in silico inhibitory action studies of azo-anchored imidazo[4,5-b]indole scaffolds against the COVID-19 main protease (Mpro)

The present work elicits a novel approach to combating COVID-19 by synthesizing a series of azo-anchored 3,4-dihydroimidazo[4,5-b]indole derivatives. The envisaged methodology involves the l-proline-catalyzed condensation of para-amino-functionalized azo benzene, indoline-2,3-dione, and ammonium acetate precursors with pertinent aryl aldehyde derivatives under ultrasonic conditions. The structures of synthesized compounds were corroborated through FT-IR, 1H NMR, 13C NMR, and mass analysis data. Molecular docking studies assessed the inhibitory potential of these compounds against the main protease (Mpro) of SARS-CoV-2. Remarkably, in silico investigations revealed significant inhibitory action surpassing standard drugs such as Remdesivir, Paxlovid, Molnupiravir, Chloroquine, Hydroxychloroquine (HCQ), and (N3), an irreversible Michael acceptor inhibitor. Furthermore, the highly active compound was also screened for cytotoxicity activity against HEK-293 cells and exhibited minimal toxicity across a range of concentrations, affirming its favorable safety profile and potential suitability. The pharmacokinetic properties (ADME) of the synthesized compounds have also been deliberated. This study paves the way for in vitro and in vivo testing of these scaffolds in the ongoing battle against SARS-CoV-2.

Synthesis and molecular recognition characteristics of a tetrapodal benzene cage

In this contribution, we describe the preparation and recognition characteristics of a novel tetrapodal benzene cage (1). The cage can express a wide recognition range without losing selectivity for the object of appropriate size and functional groups. The key to obtaining the desired structural isomer of 1 is the synthesis and isolation of the o-bis(bromomethyl)benzene precursor (5). Three distinct guests, F− (extremely small size), d-lactate (appropriate size) and l-Asp (branched shape), were selected as examples to demonstrate the recognition characteristics of 1. By NMR titration studies, they all expressed good binding affinity (K > 105 L/mol) in competitive medium (10% DMSO/THF), indicating that 1 has a wide recognition scope. The highest binding constant was observed for d-lactate, revealing that 1 has good selectivity for d-lactate versus F− and l-Asp. Moreover, the NMR titration study of F− in DMSO indicates 1 can achieve different binding modes (1:1 and 2:1 guest-host) for small-sized guests, which allows for the further development of binary binding properties and thereafter applications in the field of catalysis.

Enhancing Graphitic Carbon Precursors from Coal Pyrolysis: A Comparative Analysis of Microwave Plasma and Conventional Thermal Upgradation Methods.

This study investigates and compares the efficacy of conventional thermal pyrolysis and microwave (MW) plasma pyrolysis in upgrading coal-derived precursors. Coal samples presenting a range of ranks were pyrolyzed under various reactive and nonreactive atmospheres using a pyroprobe, with the pyrolyzates analyzed by gas chromatography-mass spectrometry (GC-MS). Comparative MW plasma tests were conducted using a modified countertop MW unit, with condensed products similarly analyzed by GC-MS. A predominant coal devolatilization product-benzene was selected for analyzing the reactive MW plasma upgradation. Results demonstrate that conventional thermal pyrolysis lacks effectiveness in upgrading the precursors. To gain insight into the underlying reasons, chemical kinetic simulations were conducted. Oppositely, reactive MW plasma pyrolysis demonstrated remarkable precursor upgradation. These condensed MW plasma pyrolysis products were then subjected to a carbonization and graphitization heat-treatment with a comprehensive graphitic quality assessment conducted using X-ray diffraction and transmission electron microscopy. After graphitization, the MW plasma-upgraded precursor produced a carbon with a crystallite size several times greater than that of the initial benzene. By MW plasma processing, the poorly graphitizable benzene precursor was transformed into a highly graphitizable precursor comparable to coal tar pitch. The underlying reasons for this significant improvement were investigated by analyzing the compositional changes in the precursor under various reactive environments.

Synthesis of Thiophene‐fused Helicenes

AbstractThe synthesis of three penta‐ and three hexahelicenes containing two terminal thiophene units is described. The syntheses of pentahelicenes consist of 1,4‐bisalkynylation of a benzene precursor and double Suzuki coupling in 2,3‐position to introduce thiophene units. The ortho,ortho’ fusion yielding the final products was achieved with Fürstner's protocol using platinum(II) chloride or JohnPhos‐complexed gold(I) as catalysts. A similar approach to hexahelicenes started with a naphthalene derivative, where 2,7‐bisalkynylation and subsequent double Suzuki coupling with thiophene‐2‐boronic acid at 1,8‐position furnished precursors, in which ortho,ortho’ fusion to the respective hexahelicenes was achieved with platinum(II) chloride or, favourably, with indium(III) chloride. UV/Vis spectra and cyclic voltammograms were recorded for all helicenes and HOMO/LUMO gaps were calculated with DFT methods.

Real-space imaging of a phenyl group migration reaction on metal surfaces

The explorations to extend present chemical synthetic methods are of great importance to simplify synthetic routes of chemical species. Additionally, understanding the chemical reaction mechanisms is critical to achieve controllable synthesis for applications. Here, we report the on-surface visualization and identification of a phenyl group migration reaction of 1,4-dimethyl-2,3,5,6-tetraphenyl benzene (DMTPB) precursor on Au(111), Cu(111) and Ag(110) substrates. With the combination of bond-resolved scanning tunneling microscopy (BR-STM), noncontact atomic force microscopy (nc-AFM) and density functional theory (DFT) calculations, the phenyl group migration reaction of DMTPB precursor is observed, forming various polycyclic aromatic hydrocarbons on the substrates. DFT calculations reveal that the multiple-step migrations are facilitated by the hydrogen radical attack, inducing cleavage of phenyl groups and subsequent rearomatization of the intermediates. This study provides insights into complex surface reaction mechanisms at the single molecule level, which may guide the design of chemical species.

Effects of oxygen partial premixing on soot formation in ethylene counterflow flames with oscillating strain rates

The sooting characteristics of counterflow partially-premixed flames subject to monochromatic oscillation of strain rates were investigated. Strain rate oscillations with well controlled frequencies and amplitudes were imposed on a series of ethylene counterflow partially-premixed flames. Flow fields and soot volume fractions were measured non-intrusively in a spatially and temporally resolved manner. Numerical simulations were also performed to support the experimental observations. The results showed that oxygen partial premixing in the ethylene fuel stream notably increased soot production due to the enhanced temperature and oxidative pyrolysis that led to increased formation of benzene precursors. More importantly, despite these enhancing effects on soot loading, we demonstrated for the first time that partial premixing does not alter the sensitivity of soot formation to strain rate in steady counterflow flames. In addition, when subject to oscillating strain rates, the unsteady responses of partially-premixed flames were still seen to be independent of partial premixing. This indicates that our previous conclusion—the sensitivity of soot formation to strain rate in steady counterflow diffusion non-premixed flames determines its response under unsteady condition—still holds for partially-premixed flames. The results could be useful for the development of advanced flamelet model to quantitatively account for unsteady effects on soot formation in practical turbulent flames that frequently encounters partial premixing.

Hyper-crosslinked polymers with controlled multiscale porosity for effective removal of benzene from cigarette smoke

Abstract A series of hyper-crosslinked polymers (HCPs) with connected hierarchical porous structures were synthesized from phenyl-based precursors of benzene (BEN), benzyl alcohol, aniline, biphenyl, and 1,3,5-triphenylbenzene (TPB) via the knitting method. The porous structures of the HCPs were greatly influenced by substituent groups and BEN ring number in the precursors. HCPs prepared from TPB had the largest surface area and pore volume with multiscale porosity. The porous structure of the HCPs could also be adjusted by the crosslinker amount. Insufficient crosslinking led to incomplete pore architecture, while excessive crosslinking resulted in a considerable decrease in the pore volume. With these HCPs as adsorbents, the BEN yield in the cigarette smoke could be largely reduced due to the connected multiscale porosity and π–π aromatic stacking interaction that facilitated the smoke aerosol passing and the small aromatic molecules absorbing, showing great potential of these HCPs as adsorbents for effective removal of BEN from cigarette smoke.

Experimental and Numerical Study on the Sooting Behaviors of Furanic Biofuels in Laminar Counterflow Diffusion Flames

Furanic biofuels have received increasing research interest over recent years, due to their potential in reducing greenhouse gas emissions and mitigating the production of harmful pollutants. Nevertheless, the heterocyclic structure in furans make them readily to produce soot, which requires an in-depth understanding. In this study, the sooting characteristic of several typical furanic biofuels, i.e., furan, 2-methylfuran (MF), and 2,5-dimethylfuran (DMF), were investigated in laminar counterflow flames. Combined laser-based soot measurements with numerical analysis were performed. Special focus was put on understanding how the fuel structure of furans could affect soot formation. The results show that furan has the lowest soot volume fraction, followed by DMF, while MF has the largest value. Kinetic analyses revealed that the decomposition of MF produces high amounts of C3 species, which are efficient benzene precursors. This may be the reason for the enhanced formation of polycyclic aromatic hydrocarbons (PAHs) and soot in MF flames, as compared to DMF and furan flames. The major objectives of this work are to: (1) understand the sooting behavior of furanic fuels in counterflow flames, (2) elucidate the fuel structure effects of furans on soot formation, and (3) provide database of quantitative soot concentration for model validation and refinements.

Ultrafine Particulate Matter in Methane-Air Premixed Flames With Oxygen Enrichment

A complementary computational and experimental study is carried out on the formation of ultrafine particulate matter in premixed laminar methane air flames. Specifically, soot formation is examined in premixed stretch-stabilized flames to observe soot inception and growth at relatively high flame temperatures common to oxygen enriched applications. Particle size distribution functions (PSDF) measured by mobility sizing show clear trends as the equivalence ratio increases from Φ = 2.2 to Φ = 2.4. For a given equivalence ratio, the measured distribution decreases in median mobility particle size as the maximum flame temperature increases from approximately 1,950–2,050 K. The median mobility particle size is 20 nm or less for all flame conditions studied. The volume fraction decreases with increasing flame temperature for all equivalence ratio conditions. The Φ = 2.2 condition is close to the soot inception limit and both number density and volume fraction decrease monotonically with increasing flame temperature. The higher equivalence ratio conditions show a peak in number density at 2,000 K which may indicate competing soot inception processes are optimized at this temperature. Flame structure computations are carried out using detailed gas-phase combustion chemistry of the Appel, Bockhorn, Frenklach (ABF) model to examine the connection of the observed PSDF to soot precursor chemistry. Agreement between measured and computed flame standoff distances indicates that the ABF model could provide a reasonable prediction of the flame temperature and soot precursor formation for the flames currently studied. To the first order, the trends observed in the measured PSDF could be understood in terms of computed trends for the formation of benzene, naphthalene and other soot precursors. Results of the current study inform particulate matter behavior for methane and natural gas combustion applications at elevated temperature and oxygen enriched conditions.

Preparation and Characterization of Graphene from Refined Benzene Extracted from Low-Rank Coal: Based on the CVD Technology.

Industrial preparation of graphene has been a research hotspot in recent years. Finding an economical and practical carbon source and reducing the cost of production and instrument is significant in industrial graphene production. Coal is a common carbon source. Efficient improvement and utilization in the cleaning of coal has recently been a popular research area. In this study, we developed a set of graphene preparation methods based on Anhui Huainan’s low-rank gas coal (HNGC). Using self-built experimental equipment, benzene precursor was prepared from HNGC and used as carbon source to realize graphene growth. The quality of the graphene was characterized by a high-resolution microscope and Raman spectrometer. This study provides a new idea and method for the preparation of low-rank coal-based graphene.

Принцип предфракционирования в схеме разделения бензиновой фракции

The requirements to motor fuels are tightened, in particular, restrictions on the content of hydrocarbons and benzene, with the adoption of new emission standards in the modern oil refining industry. At many Russian refineries problem of benzene content decreasing in reformate, which is the main component of gasolines, and, consequently, problem of benzene content decreasing in commercial gasoline, is solved by increasing the initial boiling point of the feedstock for catalytic reforming units to 100°C. At the same time, the main benzene-forming components have boiling points up to 85˚С. This approach is explained by the limitations of technological equipment and a significant increase in energy consumption when creating proper sharpness of rectification at CDU units, while it has a negative impact on the refinery economic efficiency. The article is devoted to approach to modernization of the typical straight-run naphtha distillation unit, configured to the maximum extraction of feedstock for catalytic reforming unit while meeting the requirements imposed on the content of benzene and benzene precursors in it. The proposed solutions can be implemented in the unit current configuration and do not require replacement of main process equipment. Changes in material balance and utility consumption of the unit after described modernization are presented.

Isomer-specific speciation behaviors probed from premixed flames fueled by acetone and propanal

Chemical structures of low-pressure premixed flames respectively fueled by two C3 carbonyl isomers, acetone and propanal, at different equivalence ratios (1.0 and 1.5) were experimentally investigated in this work. Detailed speciation information was obtained by employing molecular-beam mass spectrometry with tunable synchrotron photoionization. A detailed kinetic model including the chemistry of acetone and propanal was developed and tested with the current flame speciation measurements. By combining experimental observations and modeling interpretations, comparisons were made regarding fuel-specific reaction pathways and the resulting different species pools. Some fuel-specific intermediates were detected and quantified in this work, such as ketene in acetone flames and methylketene in propanal flames. Particularly, the quantitative speciation measurements of ketene, an important primary intermediate of acetone, were satisfactorily predicted by the current model, which included an updated ketene sub-mechanism. Major efforts in this work were devoted to gaining some insights into the effects of the carbonyl position in fuel molecules on the speciation behaviors under premixed flame conditions. Carbonyl functionalities in the two C3 carbonyl compounds are tightly bonded and preferably preserved in CO. Due to the different position of the CO bond in the two isomers, the oxidation of propanal leads to abundant ethyl as a chain carrier, while the acetone consumption easily results in a significant amount of methyl, an inhibitor on the fuel reactivity. As a result, higher reactivity of propanal was observed. More importantly, the different fuel consumption patterns also influence the speciation behaviors. Specifically, the larger concentration of benzene precursors such as allyl, was observed in the propanal flames. Besides, typical oxygenated emissions formaldehyde and acetaldehyde had more remarkable concentrations in acetone and propanal flames, respectively.

Flexible Al2O3/plasma polymer multilayer moisture barrier films deposited by a spatial atomic layer deposition process

Al2O3/plasma polymer multilayers were developed and characterized for the moisture barrier films of flexible organic devices. The inorganic Al2O3 thin films were deposited by a spatial atomic layer deposition process and the organic layers were deposited by plasma polymerization in the same chamber using CHF3, benzene, and cyclohexane precursors. The deposition rate, light transmittance, and surface roughness of the plasma polymer films obtained from the three precursors were investigated. The three plasma polymer layers were introduced between Al2O3 layers and their effect on the water permeability and flexibility of each Al2O3/plasma polymer multilayer structure was evaluated. The multilayer structure with hydrocarbon from cyclohexane shows better flexibility than that with fluorocarbon by CHF3 and hydrocarbon by benzene. Polymer interlayers with plasma thicker than 20 nm are necessary for reasonable flexibility. The authors increased the number of layers up to 21 to improve the water permeability and flexibility. The water vapor transmission rate (WVTR) of a 100 nm-thick Al2O3/plasma polymer was reduced to 8.5 × 10−5 g/m2 day with the 21-layer structure. This WVTR value is 58% lower than that of the 100 nm-thick single-layer Al2O3. The WVTR of a 100 nm-thick single-layer Al2O3 increased by 900% when it was bent 1000 times with a bending radius of 1 cm due to film cracks, while, under the same conditions, the 21-layer structure showed only a 32% increase in the WVTR. These results indicate that the nanometer-scale-thick plasma polymer can be an effective solution for multilayer moisture barrier films.

On-Surface Dehydro-Diels-Alder Reaction of Dibromo-bis(phenylethynyl)benzene.

On-surface synthesis under ultrahigh vacuum conditions is a powerful tool to achieve molecular structures that cannot be accessed via traditional wet chemistry. Nevertheless, only a very limited number of chemical reactions out of the wide variety known from solution chemistry have been reported to proceed readily on atomically flat substrates. Cycloadditions are a class of reactions that are particularly important in the synthesis of sp2-hybridized carbon-based nanostructures. Here, we report on a specific type of [4 + 2] cycloaddition, namely, a dehydro-Diels-Alder (DDA) reaction, performed between bis(phenylethynyl)-benzene precursors on Au(111). Unlike a Diels-Alder reaction, DDA exploits ethynyl groups to achieve the formation of an extra six-membered ring. Despite its extensive use in solution chemistry for more than a century, this reaction has never been reported to occur on surfaces. The specific choice of our precursor molecule has led to the successful synthesis of benzo- and naphtho-fused tetracene and heptacene products bearing styryl groups, as confirmed by scanning tunneling microscopy and noncontact atomic force microscopy. The two products arise from dimerization and trimerization of the precursor molecules, respectively, and their observation opens perspectives to use DDA reactions as a novel on-surface synthesis tool.

Stepwise Synthesis of Tetra-imidazolium Macrocycles and Their N-Heterocyclic Carbene Metal Complexes.

A modular stepwise synthetic method has been developed for the preperation of tetra-imidazolium macrocycles. Initially a series of three bis(imidazolylmethyl)benzene precursors were alkylated with 1,2-dibromoethane to produce the corresponding bis-bromoethylimidazolium bromide salts. In the second step the bis-bromoethylimidazolium bromide salts were reacted with selected bis(imidazolylmethyl)benzene molecules to produce a series of two symmetrical and three asymmetrical tetra-imidazolium macrocycles. These tetra-imidazolium salts act receptors for anions and 1H-NMR titration studies were used to determine the association constants between two of the macrocycles and the halide anions chloride, bromide and iodide. The tetra-imidazolium salts are precursors for N-heterocyclic carbene (NHC) ligands and the corresponding silver(I), gold(I), and palladium(II) NHC complexes have been prepared. Varied structures were obtained, which depend on the chosen macrocyclic ligand and metal ion and in the case of the coinage metals Ag(I) and Au(I), mono, di, and hexanuclear complexes were formed.

Synthesizing Highly Regular Single-Layer Alkynyl-Silver Networks at the Micrometer Scale via Gas-Mediated Surface Reaction.

Extended organometallic honeycomb alkynyl-silver networks have been synthesized on a noble metal surface under ultrahigh vacuum conditions via a gas-mediated surface reaction protocol. Specifically, the controlled exposure to molecular oxygen efficiently deprotonates terminal alkyne moieties of 1,3,5-tris(4-ethynylphenyl)benzene (Ext-TEB) precursors adsorbed on Ag(111). At Tsub = 200 K, this O2-mediated reaction pathway features high chemoselectivity without poisoning the surface. Through mild annealing to 375 K, long-range ordered alkynyl-silver networks incorporating substrate atoms evolve, featuring Ag- bis-acetylide motifs, high structural quality and a regular arrangement of nanopores with a van der Waals cavity of ≈8.3 nm2.

The Role of Kinetics versus Thermodynamics in Surface-Assisted Ullmann Coupling on Gold and Silver Surfaces.

Surface-assisted Ullmann coupling is the workhorse of on-surface synthesis. Despite its obvious relevance, many fundamental and mechanistic aspects remain elusive. To shed light on individual reaction steps and their progression with temperature, temperature-programmed X-ray photoelectron spectroscopy (TP-XPS) experiments are performed for a prototypical model system. The activation of the coupling by initial dehalogenation is tracked by monitoring Br 3d core levels, whereas the C 1s signature is used to follow the emergence of metastable organometallic intermediates and their conversion to the final covalent products upon heating in real time. The employed 1,3,5-tris(4-bromophenyl)benzene precursor is comparatively studied on Ag(111) versus Au(111), whereby intermolecular bonds and network topologies are additionally characterized by scanning tunneling microscopy (STM). Besides the well-comprehended differences in activation temperatures for debromination, the thermal progression shows marked differences between the two surfaces. Debromination proceeds rapidly on Ag(111), but is relatively gradual on Au(111). While on Ag(111) debromination is well explained by first-order reaction kinetics, thermodynamics prevail on Au(111), underpinned by a close agreement between experimentally deduced and density functional theory (DFT) calculated reaction enthalpies. Thermodynamically controlled debromination on Au(111) over a large temperature range implies an unexpectedly long lifetime of surface-stabilized radicals prior to covalent coupling, as corroborated by TP-XPS of C 1s core levels. These insights are anticipated to play an important role regarding our ability to rationally synthesize atomically precise low-dimensional covalent nanostructures on surfaces.

X-ray absorption anomaly of well-characterized multiwall carbon nanotubes

We studied X-ray absorption of multiwall carbon nanotube (MWCNT) produced by the chemical vapor deposition method using ethanol and benzene precursors at 1473 K with X-ray absorption fine structure in order to obtain a new designing direction for X-ray shielding fabrics. Acid oxidation and thermal annealing further treated the MWCNTs. The energy dependence of X-ray absorptivity of MWCNTs was efficiently used to remove the effect of the metallic impurity contribution, to elucidate the relationship between X-ray mass attenuation coefficient and the structure of MWCNT. The thermal annealing treatment at 2773 K was the most effective method to increase the crystallinity and to remove the impurities of MWCNTs. The acid and oxidation treated MWCNT induced not only the surface structure difference between MWCNT and highly oriented pyrolytic graphite (HOPG) but also the addition of surface oxygen related functional groups from those treatments, which influence the mass attenuation coefficient (μ/ρ). The X-ray absorptivity of heat treated E-MWCNT and B-MWCNT at 2773 K was close to that of HOPG indicating that those MWCNTs have a well-ordered crystal structure, quite similar to HOPG. On the other hand, E-MWCNT having a less-crystalline surface structure showed larger X-ray absorptivity than HOPG by about 9%.

On-surface synthesis of one-type pore single-crystal porous covalent organic frameworks.

Employing a 1,3,5-tris(4-bromophenyl)benzene precursor as a building block, we successfully fabricate large-scale, non-multihole and single-layer pCOFs on the Ag(111) surface in a controllable manner via the on-surface reaction. We reveal that two main factors, the heating rate and growth temperature, have a strong impact on the size and quality of the pCOFs by STM. Furthermore, the band gap of the pCOFs has been further measured to be approximately 3.01 eV.

Influence of n-Butanol Addition on C3H3 Formation in n-Butane Combustion

The effects of different n-butanol blending ratios (Rb) on the formation of propargyl radical (C3H3), an important benzene precursor, during the combustion of n-butanol/n-butane blends are studied. A detailed kinetic combustion model of n-butanol/n-butane is developed and the premixed n-butanol/n-butane flames are calculated at an equivalence ratio of 1.5, an initial pressure of 1.0 atm, and a temperature range from 800 to 2000 K in a perfectly stirred reactor (PSR), with Rb varying from 0 to 1.0. The results show that under the investigated conditions, the peak value of the mole fraction of C3H3 decreases non-linearly with the increase of Rb. Due to the interaction between combustion products of n-butane and n-butanol during the combustion process, the actual peak mole fraction of C3H3 is higher than the theoretical value. A rate of production (ROP) analysis reveals that the number of β-carbon atoms in the molecule of n-butane and n-butanol affects the efficiency of H-abstraction reactions in generating 2-butyl (sC4H9) and C4H8OH-3 (CH3–*CH–CH2–CH2–OH), which are the two major original sources of C3H3. For both n-butane and n-butanol, the main pathway of forming C3H3 from propene (C3H6) is basically the same, which is C3H6 → C3H5-a (symmetric allyl radical) → C3H4-a (allene) → C3H4-p (propyne) → C3H3. When Rb ranges from 0.4 to 0.6, the deviation degrees of the peak mole fraction of the involved C3 species reach a maximum, indicating that the interaction between the two fuels is the most significant. The non-linear decrease in the mole fraction of C3H3 can attribute to three reasons: (a) the increase of Rb promotes the increase of the conversion ratios of n-butane to sC4H9 and n-butanol to C4H8OH-3; (b) the contribution ratios of the reactions involved in the C3H5-a → C3H4-a → C3H4-p → C3H3 pathway decrease with increasing Rb; (c) C3H5-t (tertiary allyl radical) → C3H4-p → C3H3 is the secondary pathway for the formation of C3H3. With the increase of Rb, the dependence of C3H4-p on C3H5-t increases and the conversion ratio of C3H5-t to C3H4-p increases. This study investigates the non-linear decrease of the mole fraction of C3H3 by revealing the interactions between n-butanol and n-butane during the combustion, which can help better understand the effect of n-butanol on the formation of benzene.