Aromaticity Index Research Articles

Insight into the role of binding interaction in the transformation of tetracycline and toxicity distribution

The transformation of free state organic micro-pollutants (MPs) has been widely studied; however, few studies have focused on mixed and bound states MPs, even though numerous ionizable organic MPs process a strong tendency to combine with dissolved organic matters in aquatic environments. This study systemically investigated the distribution and toxicity assessment of tetracycline (TET) transformation products in free, mixed and bound states during UV, UV/H2O2, UV/PS and CNTs/PS processes. A total of 33 major transformation products were identified by UPLC-Q-TOF-MSMS analysis, combining the double bond equivalence and aromaticity index calculations. The binding interaction would weaken the attack on the dimethylamino (-N(CH3)2) group and induce the direct destruction of rings A and B of TET through the analysis of 2D Kernel Density changes and density functional theory (DFT) calculations. Toxicity assessment and statistics revealed that the intermediate products with medium molecular weight (230≤ m/z ≤ 380) exhibited higher toxicity, which was closely related to the number of the rings in molecular structures (followed as 2»3 > 1≈4). A predicted toxicity accumulation model (PTAM) was established to evaluate the overall toxicity changes during various oxidation processes. This finding provides new insight into the fate of bound MPs during various oxidation processes in the natural water matrix.

Assessment of the Performance of the Bond Resonance Energy, Circuit Resonance Energy, Magnetic Resonance Energy, Ring Currents, and Aromaticity of Anthracene, Biphenylene, Phenalenyl, and p-Terphenyl.

This paper contributes to the further understanding of bond resonance energy (BRE), circuit resonance energy (CRE), and ring currents (RC = I) as indices for the measure of local ring aromaticity and topological resonance energy (TRE) and magnetic resonance energy (MRE) as indices for the measure of global molecular aromaticity. Calculations of ring currents in the 3-ring polycyclic hydrocarbons of anthracene, biphenylene, phenalenyl, and p-terphenyl are demonstrated. This comparative study provides new molecular insights. A number of shortcut techniques are briefly illustrated. p-Terphenyl is a benzenoid total resonant sextet (TRS) and biphenylene is shown to be a nonbenzenoid TRS, i.e., both obey Clar's sextet principle. p-Terphenyl has only ring circuits, whereas anthracene, biphenylene, and phenalenyl have ring circuits and larger circuits engulfing the ring circuits. The perimeter circuits of anthracene, biphenylene, and phenalenyl engulf all other circuits, thus leading to the definition of MRE. By these several aromatic indices, the monocation, monoanion, and monoradical of phenalenyl are equally aromatic. The agreement in the prediction of local ring aromaticity between the three indices of m-BRE, t-BRE, and CRE is evaluated.

Bulk Chemical and Optical Spectroscopy Characterisations of Dissolved Organic Matter Extracted from the Tropical Coastal Sediment

The study of organic matter characterisation in coastal sediment is useful for understanding how dissolved organic matter (DOM) reactivity influences the fate of pollutants in the aquatic environment. However, there is little information available on the structural properties of DOM in coastal sediment. Chemical analysis, UV-Visible (UV-Vis) absorbance, fluorescence, and Fourier-transform infrared (FTIR) spectroscopy were used in this work to characterise and compare the components of water-extractable organic matter (WEOM) fractions from sediment from an estuary, a coastal area, and a port in Peninsular Malaysia, Malaysia. The elemental analysis (H/C and C/N ratios) of the three samples differed, which coincided with the findings of optical indices estimated from UV-Visible and fluorescent spectroscopy analyses. WEOM had an average output of 7.05 to 8.47 mg/L and was very dominating with heavy fraction organic carbon (HFOC). In DOM-KS and DOM-K sediments, the allochthonous component with a high degree of condensation and the aromatic compound was the dominating composition. Meanwhile, the DOM-KT possessed a high autochthonous composition as well as carboxylic and phenolic content. Correlation analysis indicates that the aromaticity index SUVA254 and humification index (HIX) have positive correlations. The combined results of the chemical and spectroscopic analyses indicate that different coastal ecosystems, with the integration of various human and land activities, produce variations in DOM in the coastal area.

Plant-Derived and Dietary Hydroxybenzoic Acids-A Comprehensive Study of Structural, Anti-/Pro-Oxidant, Lipophilic, Antimicrobial, and Cytotoxic Activity in MDA-MB-231 and MCF-7 Cell Lines.

Seven derivatives of plant-derived hydroxybenzoic acid (HBA)—including 2,3-dihydroxybenzoic (2,3-DHB, pyrocatechuic), 2,4-dihydroxybenzoic (2,4-DHB, β-resorcylic), 2,5-dihydroxybenzoic (2,5-DHB, gentisic), 2,6-dihydroxybenzoic (2,6-DHB, γ-resorcylic acid), 3,4-dihydroxybenzoic (3,4-DHB, protocatechuic), 3,5-dihydroxybenzoic (3,5-DHB, α-resorcylic), and 3,4,5-trihydroxybenzoic (3,4,5-THB, gallic) acids—were studied for their structural and biological properties. Anti-/pro-oxidant properties were evaluated by using DPPH• (2,2-diphenyl-1-picrylhydrazyl), ABTS•+ (2,2-azino-bis(3-ethylbenzothiazoline-6-sulfonic acid), FRAP (ferric-reducing antioxidant power), CUPRAC (cupric-reducing antioxidant power), and Trolox oxidation assays. Lipophilicity was estimated by means of experimental (HPLC) and theoretical methods. The antimicrobial activity against Escherichia coli (E. coli), Pseudomonas aeruginosa (P. aeruginosa), Staphylococcus aureus (S. aureus), Bacillus subtilis (B. subtilis), Salmonella enteritidis (S. enteritidis), and Candida albicans (C. albicans) was studied. The cytotoxicity of HBAs in MCF-7 and MDA-MB-231 cell lines was estimated. Moreover, the structure of HBAs was studied by means of experimental (FTIR, 1H, and 13C NMR) and quantum chemical DFT methods (the NBO and CHelpG charges, electrostatic potential maps, and electronic parameters based on the energy of HOMO and LUMO orbitals). The aromaticity of HBA was studied based on the calculated geometric and magnetic aromaticity indices (HOMA, Aj, BAC, I6, NICS). The biological activity of hydroxybenzoic acids was discussed in relation to their geometry, the electronic charge distribution in their molecules, their lipophilicity, and their acidity. Principal component analysis (PCA) was used in the statistical analysis of the obtained data and the discussion of the dependency between the structure and activity (SAR: structure–activity relationship) of HBAs. This work provides valuable information on the potential application of hydroxybenzoic acids as bioactive components in dietary supplements, functional foods, or even drugs.

Push–Pull Effect on the Gas-Phase Basicity of Nitriles: Transmission of the Resonance Effects by Methylenecyclopropene and Cyclopropenimine π-Systems Substituted by Two Identical Strong Electron Donors

The gas-phase basicity of nitriles can be enhanced by a push–pull effect. The role of the intercalated scaffold between the pushing group (electron-donor) and the pulling (electron-acceptor) nitrile group is crucial in the basicity enhancement, simultaneously having a transmission function and an intrinsic contribution to the basicity. In this study, we examine the methylenecyclopropene and the N-analog, cyclopropenimine, as the smallest cyclic π systems that can be considered for resonance propagation in a push–pull system, as well as their derivatives possessing two strong pushing groups (X) attached symmetrically to the cyclopropene scaffold. For basicity and push–pull effect investigations, we apply theoretical methods (DFT and G2). The effects of geometrical and rotational isomerism on the basicity are explored. We establish that the protonation of the cyano group is always favored. The push–pull effect of strong electron donor X substituents is very similar and the two π-systems appear to be good relays for this effect. The effects of groups in the two cyclopropene series are found to be proportional to the effects in the directly substituted nitrile series X–C≡N. In parallel to the basicity, changes in electron delocalization caused by protonation are also assessed on the basis of aromaticity indices. The calculated proton affinities of the nitrile series reported in this study enrich the gas-phase basicity scale of nitriles to around 1000 kJ mol−1.

Forest land-use increases soil organic carbon quality but not its structural or thermal stability in a hedgerow system

How land-use and soil depth affect soil organic carbon (SOC) quality and stability, properties that are key to the long-term storage of C, is poorly understood in agroforestry systems. We examined the effects of land-use (forest vs. annual cropland) and soil depth (0–10 vs. 10–30 cm) on the quality (availability of C for decomposition), structural stability (composition of C functional groups), and thermal stability (energy yield and temperature characteristics during thermal oxidation) of SOC in a hedgerow system in central Alberta, using solid-state 13C nuclear magnetic resonance (NMR) spectroscopy and thermal analysis methods. The SOC quality (proportion of O-alkyl C) was higher, while the proportion of H- and C-substituted aromatic C and structural stability (hydrophobicity index (HB/HI), aromaticity index (ARM), and alkyl index (A/OA)) were all lower in the forest than in the cropland. The SOC also had lower thermal stability (higher energy density and lower temperature at which 50% of the mass was lost (TG-T50)) in the forest than in the cropland. Between the two soil depths, SOC quality (proportion of N-alkyl C, O-alkyl C and di-O-alkyl C) was higher, but the proportion of H- and C-substituted aromatic C and structural and thermal stabilities were lower, within the surficial 0–10 cm layer than in the 10–30 cm soil. We conclude that while the forest land-use within the hedgerow system had a higher SOC quality, it had lower SOC structural and thermal stabilities, suggesting that SOC under the forest land-use may be more susceptible to decline under climate change or other forms of anthropogenic disturbance.

Molecular structure, spectroscopy and photochemistry of alprazolam

In this article, a comprehensive study of the molecular structure, spectroscopy, and photochemistry of alprazolam (Xanax®; 8-chloro-1-methyl-6-phenyl-4H-[1,2,4]triazolo[4,3-a][1,4]benzodiazepine) is reported. The structure of the isolated molecule of the compound was investigated using density functional theory (DFT), revealing that the molecule exists in a single conformer, which is associated with 12 equivalent-by-symmetry minima. The molecules of the compound were trapped from the gas phase into a low temperature (10 K) argon matrix, and the infrared (IR) spectrum of the matrix-isolated monomers was obtained and assigned. The matrix-isolated molecules were then subjected to in situ ultraviolet (UV) irradiation. It was concluded that alprazolam is photostable under these experimental conditions, contrarily to what is known to happen for the compound in solution or in solid state in the presence of excipients used in the pharmaceutical formulations. An explanation for the photostability of the matrix-isolated compound is provided, based on rapid recombinations of the biradical formed from the UV-induced diazepine ring cleavage or the chlorine atom and the complementary radical resulting from the scissoring of the C–Cl bond, which are favored by the cage confinement of the matrix-isolated molecules. The major fragmentation channels of the alprazolam molecule upon electron bombardment (70 eV) were determined by analysis of its electron ionization mass spectrum, which reveals that the major primary fragmentation processes lead to formation of cyanobenzene, N2, HCl (Cl2), and benzene.The compound was also investigated in solution by multinuclear (1H, 13C and 15N) nuclear magnetic resonance (NMR) and ultraviolet (UV) spectroscopies, and in crystalline phase (P-1 polymorph) through IR and Raman spectroscopies. In addition, the structure of the crystal, previously reported in the literature [M. R. Caira, B. Easter, S. Honiball, A. Horne and L. R. Nassimbeni, Structure and Thermal Stability of Alprazolam and Selected Solvates, J. Pharm. Sci., 1995, 84, 1379–1384], was revisited in order to evaluate the relative importance of the different types of intermolecular interactions, using Hirshfeld surface analysis, the CE-B3LYP energy decomposition model, and the harmonic oscillator model of aromaticity (HOMA) index. Finally, the enthalpy of sublimation of the crystal was estimated from the CE-B3LYP calculated lattice energy.

Gas-phase acidities of organic acids based on 9H-fluorene scaffold: a DFT study

The density functional theory (DFT) calculations have been performed on a new set of organic Brønsted acids based on 9H-fluorene scaffold. The optimal structures and acidity of the compounds have been calculated by using DFT/B3LYP/6–31 + + G(d,p) computational method. The acidity of the designed compounds was obtained in the range of 276–328 kcal/mol that the fluorene scaffold bearing ketenimine group 17 and trifilic group 20 with ΔHacid of 276.3 and 285.4 kcal/mol, respectively, were found to be within the range of superacids, being more acidic than simple fluorene and mineral acids. The designed compounds and the corresponding conjugate bases were also examined from the aromaticity indices point of view. The tautomerization process for some designed structures was investigated by DFT calculations. Molecular electrostatic potential analysis for the designed acids and the corresponding conjugate bases was also used for charge distribution analysis.

Covalence and π-electron delocalization influence on hydrogen bonds in proton transfer process of o-hydroxy aryl Schiff bases: A combined NMR and QTAIM analysis.

Within the framework of the density functional theory approach, we studied the relationship between the chemical nature of intramolecular hydrogen bonds (HBs) and nuclear magnetic resonance (NMR) parameters, J-couplings and 1H-chemical shifts [δ(1H)], of the atoms involved in such bonds in o-hydroxyaryl Schiff bases during the proton transfer process. For the first time, the shape of the dependence of the degree of covalence in HBs on 1J(N-H), 1J(O-H), 2hJ(O-N), and δ(1H) during the proton transfer process in o-hydroxyaryl Schiff bases was analyzed. Parameters obtained from Bader's theory of atoms in molecules were used to assess the dependence of covalent character in HBs with both the NMR properties. The influence of π-electronic delocalization on 2hJ(N-O) under the proton transfer process was investigated. 2hJ(O-N) in a Mannich base was also studied in order to compare the results with an unsaturated system. In addition, substituent effects on the phenolic ring were investigated. Our results indicate that the covalent character of HBs on both sides of the transition state undergoes a smooth exponential increase as the δ(1H) moves downfield. The degree of covalence of the N⋯H (O⋯H) bond increases linearly as 1J(N-H) (1J(O-H)) becomes more negative, even after reaching the transition state. Non-vanishing values of spin dipolar (SD) and paramagnetic spin orbital terms of 2hJ(O-N) show that π-electronic delocalization has a non-negligible effect on tautomeric equilibrium and gives evidence of the presence of the resonance assisted HB.Variation of the SD term of 2hJ(O-N) follows a similar pattern as the change in the para-delocalization aromaticity index of the chelate ring.

Empirical Models to Characterize the Structural and Physiochemical Properties of Vacuum Gas Oils with Different Saturate Contents

Inter-criteria analysis was employed in VGO samples having a saturate content between 0.8 and 93.1 wt.% to define the statistically significant relations between physicochemical properties, empirical structural models and vacuum gas oil compositional information. The use of a logistic function and employment of a non-linear least squares method along with the aromatic ring index allowed for our newly developed correlation to accurately predict the saturate content of VGOs. The empirical models developed in this study can be used not only for obtaining the valuable structural information necessary to predict the behavior of VGOs in the conversion processes but can also be utilized to detect incorrectly performed SARA analyses. This work confirms the possibility of predicting the contents of VGO compounds from physicochemical properties and empirical models.

Contamination Characteristics of Surface Runoff in Densely Populated Areas in Downstream Yangtze River, China

Urban surface runoff is an important non-point pollution source, and research on contamination characteristics of runoff is urgent for improving urban aquatic environment quality. Typical cities along the downstream Yangtze River, Wuxi and Nanjing, were selected in this study, and runoff samples from various underlying surfaces were collected to investigate contamination characteristics of heavy metals and dissolved organic matter (DOM). The results indicated that the concentration of heavy metals have exceed water quality standards in underlying surfaces partly, the decreasing order of metal contaminations was Zn > Cu > Pb > Sb > Cd. Contamination characteristics of surface runoff were found to exhibit significant differences, and arterial traffic exhibited the severe contamination of both heavy metals and DOM. Spectral characteristics indicated that the structure of DOM exhibited significant differences in various underlying surfaces, and DOM humification levels in Wuxi showed the following decreasing order:roof covering > sidewalk > parking area > grassy area > arterial traffic, aromaticity indexes exhibited order as:arterial traffic > grassy area > sidewalk > roof covering > parking area. Differential absorption spectroscopy (DAS) and FT-IR analyses indicated that DOM exhibited strong combination effects with cationic metal pollutants (Cu), which mainly occur with C＝C structure and carboxylic and phenolic groups; DOM presented weak combination with anion metal pollutant (Sb), indicating that Sb likely exists as a free anion in runoff. The annual total loadings of metal contaminations in the study area were as follows:Zn > Cu > Pb > Sb > Cd. The loadings of Zn were 4.83 kg·a-1 and 3.21 kg·a-1 in Wuxi and Nanjing, respectively. Annual loadings of DOM reached 0.93 g·(m2·a)-1 and 8.72 g·(m2·a)-1. The results indicated that corresponding pollution reduction measures should be implemented for different underlying surfaces to reduce contaminant concentrations; our findings may provide essential information for improving the aquatic environment quality in downstream Yangtze River.

Synthesis, Spectroscopic, and Theoretical Study of Copper and Cobalt Complexes with Dacarbazine.

Dacarbazine (DAC) 5-(3,3-dimethyl-1-triazenyl)imidazole-4-carboxamide is an imidazole-carboxamide derivative that is structurally related to purines. DAC belongs to the triazene compounds, which are a group of alkylating agents with antitumor and mutagenic properties. DAC is a non-cell cycle specific drug, active in all phases of the cellular cycle. In the frame of this work the 3d metal complexes (cobalt and copper) with dacarbazine were synthesized. Their spectroscopic properties by the use of FT-IR, FT-Raman, and 1HNMR were studied. The structures of dacarbazine and its complexes with copper(II) and cobalt(II) were calculated using DFT methods. The effect of metals on the electronic charge distribution of dacarbazine was discussed on the basis of calculated NBO atomic charges. The reactivity of metal complexes in relation to ligand alone was estimated on the basis of calculated energy of HOMO and LUMO orbitals. The aromaticity of the imidazole ring in dacarbazine and the complexes were compared (on the basis of calculated geometric indices of aromaticity). Thermal stability of the investigated 3d-metal complexes with dacarbazine and the products of their thermal decomposition were analyzed.

Favipiravir: insight into the crystal structure, Hirshfeld surface analysis and computational study

In this work we report structural and computational studies of favipiravir, which is now used as a drug for COVID-19 treatment. The molecule is completely flat and stabilized by an intramolecular O–H···O hydrogen bond, yielding a six-membered pseudo-aromatic ring. The aromaticity index of this pseudo-aromatic ring was found to be 0.748, while the same indix for the pyrazine ring in favipiravir was found to be 0.954. The crystal packing of favipiravir is mainly constructed through intermolecular N–H···O, N–H···N and C–H···O hydrogen bonds, yielding a 3D supramolecular framework with a zst topology defined by the point symbol of (65·8). The crystal structure of favipiravir is further stabilized by weak C–F···F–C intermolecular type II dihalogen interactions, yielding a 1D supramolecular polymeric chain. More than 80% of the total Hirshfeld surface area for favipiravir is occupied by H···H/C/N/O/F and C···N/O contacts. Energy frameworks have been calculated to additionally analyze the overall crystal packing. It was established that the structure of favipiravir is mainly characterized by the dispersion energy framework followed by the less significant electrostatic energy framework contribution. Finally, by using density functional theory (DFT) calculations and the quantum theory of atoms in molecules, we have assigned the interaction energy of each hydrogen bond, which can be helpful to develop scoring functions to be used in force fields/docking calculations.

Size‐dependent Molecular Characteristics and Possible Sources of Organic Aerosols at a Coastal New Particle Formation Hotspot of East China

AbstractWe investigated size‐dependent molecular characteristics of coastal organic aerosols from <0.032 to 3.2 μm at a new particle formation (NPF) hotspot of east China by using Fourier transform‐ion cyclotron resonance mass spectrometry (FT‐ICR‐MS). Strong connection between C20–33HhOo/C18,30HhOoNn compounds in particles smaller than 0.10 μm and the volatile organic compounds emitted from local intertidal macroalgae suggests that the organic compounds (OC) in ultrafine particles are formed probably via the gas‐phase oxidation of long‐chain fatty aldehydes or acids, followed by particle‐phase accretion reactions or imine formation during the coastal NPF events. In 0.18–0.56 μm particles, dominant C8–C20 CHO, CHON, CHOS and CHONS compounds (maximum: C10 or C15) are suggested most likely to be terpene oxidation products. Highly oxygenated compounds with 0.6 ≤ H/C ≤ 1.5 and 0.67 ≤ O/C ≤ 1.2 reside mostly in 0.18–0.56 μm particles, accounting for 5% of the OC formulas in this size range. Iodinated OC are subsequently formed via electrophilic substitution of non‐iodinated OC by iodine cations (e.g., from HOI or I2) in iodine‐rich particles. CHN and Cl/Br‐containing OC account altogether for only 0.7% and 0.9% of OC formulas, respectively. As a result of the above compound distribution, the intensity weighted unsaturation degree and carbon oxidation state of OC increase with particle size. The distribution of aromatic compounds (i.e. Aromaticity Index > 0.5) is bimodal with peaks in 0.056–0.18 μm and 1.0–3.2 μm. In addition, our study observed higher unsaturation degree, carbon oxidation state and aromaticity of OC in coastal PM2.5 than inland urban PM2.5 in the same region.

Effects of Multiple OH/SH Substitution on the H‐Bonding/Stability versus Aromaticity of Benzene Rings: From Computational Insights

AbstractProperties of intramolecular H‐bond (IHB) for a chemical system can affect the changes in geometrical/electronic features in the vicinity of the bridge. Substitution of an atom (H) in benzene with OH/SH groups forming IHB has little effect on its aromaticity. This report is devoted to the depiction of the effect of OH/SH substituent on stability/aromaticity of multi‐substituted benzene ringsviaIHB formation. The computational studies on the stability/aromaticity in the homo (OH/SH) and hetero (OH and SH) substituted form of the benzene systems have been investigated using B3LYP/aug‐cc‐pVDZ and MP2/aug‐cc‐pVDZ approaches with the aid of aromaticity indices (AIs) descriptors (NICS, HOMA, AIBIC, and PDI) and IHB/stability diagnostics; relative energy, QTAIM based interaction energy acquired from the potential energy density and electron density, HBSBIC, and HOMO‐LUMO gap including NCI plots. The IHBs formed by different OH/SH substituents have a vital role as an aromaticity modulator and deploying the above‐said tools, it turns out that the cyclic 4n+2 π‐electrons delocalization is weakened/strengthened depending on the number and types of OH/SH substituents forming the IHBs. Here, all the AIs vary in a small amount and indicative of the modulator of the π‐electron structure to the substituent effectviaIHB formation. As in practical applications, the diagnostics based on different criteria do not speak with the same voice, hence interestingly, in many cases, the changes in AIs notably correlate with their stability.

Estimation of resonance assisted hydrogen bond (RAHB) energies using properties of ring critical points in some dihydrogen-bonded complexes

Intramolecular hydrogen bond (IHB) interactions have investigated in aza-boron-hydrogen rings after formation of dihydrogen bond (DHB) interactions with some substituted aza-boron-hydrogen molecules. These molecules include electron-donating and electron-withdrawing groups. The IHB energies in the dihydrogen-bonded complexes have estimated using a method based on properties of ring critical points (RCPs). There is linear relationship between results of this method and molecular tailoring approach (MTA). Geometrical parameters, spectroscopic information, electronic properties based on atoms in molecules (AIM) method, and natural bond orbital (NBO) analysis have used to find effects of DHB on strength of the IHB interaction. Moreover, aromaticity of resonance-assisted hydrogen bond (RAHB) rings have evaluated using the para delocalization index (PDI), the aromatic fluctuation index (FLU), the average two center index (ATI), and the nucleus-independent chemical shift (NICS) to find relation between π-electron delocalization (π-ED) and properties of these rings. Results show that DHB leads to increase of strength of the IHB interaction. In addition, the PDI benchmark has the best correlation with the IHB descriptors. Additionally, localized molecular orbital energy decomposition analysis (LMO-EDA) reveals that the key components of interaction energies are exchange and electrostatic energy, respectively. Finally, new relations obtained for estimation of the IHB energies based on RCP characteristics and quantum mechanical descriptors.

Impact of Deuteration and Temperature on Furan Ring Dynamics.

Despite significant progress in conformational analysis of cyclic molecules, the number of computational studies is still limited while most of that available in the literature data have been obtained long time ago with outdated methods. In present research, we have studied temperature driven conformational changes of the furan ring at three different temperatures. Additionally, the effect of deuteration on the ring dynamics is discussed; in addition, the aromaticity indices following the Bird and HOMA schemes are computed along all trajectories. Our ab initio molecular dynamic simulations revealed that deuteration has changed the furan ring dynamics and the obvious consequences; in addition, the shape and size of molecule are expected to be different.

Applications of H\xfcckel-Su-Schrieffer-Heeger method

The equilibrium carbon-carbon (C-C) bond lengths in π-electron hydrocarbons are very sensitive to the electronic ground-state characteristic. In the recent two papers by Stolarczyk and Krygowski (J Phys Org Chem, 34:e4154,e4153, 2021) a simple quantum approach, the Augmented Hückel Molecular Orbital (AugHMO) model, is proposed for the qualitative, as well as quantitative, study of this phenomenon. The simplest realization of the AugHMO model is the Hückel-Su-Schrieffer-Heeger (HSSH) method, in which the resonance integral β of the HMO model is a linear function the bond length. In the present paper, the HSSH method is applied in a study of C-C bond lengths in a set of 34 selected polycyclic aromatic hydrocarbons (PAHs). This is exactly the set of molecules analyzed by Riegel and Müllen (J Phys Org Chem, 23:315, 2010) in the context of their electronic-excitation spectra. These PAHs have been obtained by chemical synthesis, but in most cases no diffraction data (by X-rays or neutrons) of sufficient quality is available to provide us with their geometry. On the other hand, these PAHs are rather big (up to 96 carbon atoms), and ab initio methods of quantum chemistry are too expensive for a reliable geometry optimization. That makes the HSSH method a very attractive alternative. Our HSSH calculations uncover a modular architecture of certain classes of PAHs. For the studied molecules (and their fragments – modules), we calculate the values of the aromaticity index HOMA.

Study on the microscopic characteristics and rheological properties of thermal-oxidative aged and virgin-old recycled asphalts

This study aimed to investigate the thermal-oxidative aging and virgin-old recycling behavior of SBS polymer modified asphalt. For the same, the four-component method, the Fourier transform infrared spectroscopy (FTIR), and the gel permeation chromatography (GPC) test were adopted for characterizing five types of asphalt binders. Besides, Brookfield rotary viscosity and time scan tests were conducted for measuring the rheological parameters of the asphalt samples. The results indicated the following: (i) Thermal-oxidative aging deteriorated the fluidity and performance stability of the asphalt. The aromatic ring index, IC=C, was able to reflect the change in the temperature sensitivity of the asphalt during the process of aging. (ii) After thermal oxidation, the increase in viscosity was mainly attributed to the increase of asphalt macromolecules weight. A reduction in the proportion of the dispersion medium in the asphalt colloid structure was observed to be the main reason for its decreased fatigue resistance potential. (iii) By adding fresh asphalt, the virgin-old recycling approach slowed the thermal-oxidative aging, primarily due to physical integration. (iv) In this study, the asphalt viscosity-temperature properties were more sensitive to molecular changes than fatigue properties.

A Two-Step Microwave Annealing Process for PAN Pre-Oxidation through a TM-Mode Cavity.

A novel microwave annealing system and a specific processing condition are proposed for the pre-oxidation of carbon fiber. The microwave annealing system consists of a TM-mode resonant cavity and a silicon carbide (SiC) susceptor. The TM-mode cavity enhances the electric field at the center. The SiC susceptor absorbs part of the microwave energy and converts it to heat. The enhanced fields and the SiC susceptor provide both nonthermal and thermal treatments for fibrous materials with various dielectric properties. Furthermore, a two-step microwave annealing process is used to oxidize polyacrylonitrile (PAN) fiber. The scanning electron microscopy (SEM) images, differential scanning calorimetry (DSC), and X-ray diffraction (XRD) results support the theory that the microwave annealing can achieve a high aromatic index of 66.39% in just 13 min, 9 times faster than the traditional processing time. The results of the Raman spectra also illustrate that the sheath-core factor of the microwave-heated specimen is closer to one than that of the conventional furnace-heated type, which agree with the images of the cross-section area.