Aromaticity Index Research Articles

Partition of topological indices of benzenoid hydrocarbons into ring contributions

AbstractThis work presents a simple method for partitioning the bond‐additive and atoms‐pair‐additive distance‐based topological indices of plane graphs into the sum of contributions of inner faces. The proposed method is applied to decompose several topological indices (Wiener, hyper‐Wiener, Tratch‐Stankevich‐Zefirov, Balaban, and Szeged indices) into the ring contributions for a series of benzenoid systems. It was found that the employed ring partitioning scheme is providing an accurate assessment of the dominant cyclic conjugation modes in the studied benzenoid hydrocarbons. Thus, the proposed method can be used as the alternative for the quantum‐chemistry‐based aromaticity indices which are significantly more computationally demanding.

Unveiling Molecular Transformations of Soil Organic Matter after Remediation by Chemical Oxidation Based on ESI-FT-ICR-MS analysis

Remediation of soils contaminated with organic pollutants is often accomplished by chemical oxidation processes using oxidants such as persulfate or H2O2. However, it is unclear how different oxidants transform soil organic matter (SOM) and affect soil ecosystem services. Herein, two chemical oxidation technologies, Fenton reaction (FT) and base-activation of sodium persulfate (BP), were investigated to remediate diesel-polluted soils. The molecular transformation of SOM was analyzed using excitation–emission matrix fluorescence spectroscopy (EEM FS) and electrospray ionization coupled with Fourier transform ion cyclotron resonance mass spectrometry (ESI-FT-ICR-MS). Fulvic acid-like substances and lipids were consumed in both treatments, while the contents of lignin-like and tannin-like substances increased after BP treatment. The oxygen to carbon ratios (O/C), modified aromaticity index (AImod), and double bond equivalent (DBE) of SOM increased significantly in BP-treated soil, while these parameters decreased in FT-treated soil (FTS), suggesting the oxygen-containing, unsaturated and aromatic compounds were produced in BPS but removed in FTS. The increased cation exchange capacity (CEC) value (81.47 cmol/kg) and germination index of wheat seed (97%) for the SOM in BPS indicate the possible favorable effect of persulfate-based treatment on soil quality. Overall, this study advances mechanistic understanding of the effects of H2O2- and persulfate-based soil remediation technologies based on the molecular compositions of SOM and soil quality.

Making and Breaking—Insight into the Symmetry of Salen Analogues

This study focuses on selected members of the general salen-analogues family possessing two O-H⋯N hydrogen bonds, namely three isomers of N,N’-bis(salicylidene)-X-phenylenediamine, denoted as ortho, meta and para. Two of the isomers are not planar in the published crystal structures. The current study tackles the problem of symmetry and interactions within the molecules, as well as in the crystal lattice. The aromaticity of the phenyl rings is evaluated using the Harmonic Oscillator Model of Aromaticity (HOMA) index. Intra- and inter-molecular non-covalent interactions are studied via Hirshfeld surface analysis, Independent Gradient Model (IGM), Quantum Theory of Atoms in Molecules (QTAIM), Non-Covalent Interaction (NCI) index, Electron Localisation Function (ELF), Core-Valence Bifurcation (CVB) index and Symmetry-Adapted Perturbation Theory (SAPT). Density Functional Theory (DFT) simulations were carried out in vacuo and with solvent reaction field based on Polarisable Continuum Model (IEF-PCM formulation) at the ωB97XD/6-311+G(2d,2p) level. Crystal structure analyses were performed for the data reported previously in the literature. The obtained results demonstrate that the three isomers differ greatly in their structural properties (molecular symmetry is broken for the ortho and meta isomers in the solid state) and ability to form intermolecular interactions, while retaining overall similar physico-chemical characteristics, e.g., aromaticity of the phenyl rings. It was found that the presence of the polar solvent does not significantly affect the structure of the studied compounds. An application of the Hirshfeld surface analysis revealed the nature of the non-covalent interactions present in the investigated crystals. The SAPT results showed that the stability of the dimers extracted from the crystals of the Schiff base derivatives arises from electrostatics and dispersion.

Structures and solvent effects on the 1H and 13C NMR chemical shifts of the family of three pro-lithospermate molecules: DFT study

The solvent effects on the structures and nuclear magnetic resonance spectroscopy of a series of three pro-lithospermate molecules are studied. These molecules include methyl pro-lithospermate, ethyl pro-lithospermate, and n-butyl pro-lithospermate, which exhibit enantiomers and diastereoisomers. The trans-oriented enantiomers were observed by Yu et al. [Nat. Prod. Res. 31(21), 2505–2512 (2017)] and are the subject of the present study. The density functional theory was validated using the gauge-including atomic orbital/B3LYP-D3BJ/6–31++G(d,p) and continuous set of gauge transformation (CSGT)/the long-range corrected Tao, Perdew, Staroverov, and Scuseria’s τ-dependent gradient-corrected correlation-exchange functional (LC-TPSS)TPSS/cc-pVTZ methods. The chemical shifts of 1H and 13C were calculated in dimethylsulfoxide (DMSO), methanol, and water. It turns out that solvent effects are weak on the geometrical parameters (bond lengths and bond angles). The harmonic oscillator model of the aromaticity index was used to calculate the aromaticity of the subunit rings. With regard to the available experimental results, the chemical shifts of 1H and 13C are reproduced better by B3LYP-D3BJ/6–31++G(d,p) than by LC-TPSSTPSS/cc-pVTZ in the DMSO medium. The solvent effects are significant on the 13C chemical shift, mostly for protic solvents, and insignificant on 1H. The vicinal spin–spin coupling constants of protons were calculated. The coupling constant of trans-olefinic and ortho-aromatic protons fits well with the experiment.

Measurement report: Changes in light absorption and molecular composition of water-soluble humic-like substances during a winter haze bloom-decay process in Guangzhou, China

Abstract. Water-soluble humic-like substances (HULIS) absorb light in near-UV and visible wavelengths and exert significant influence on the atmospheric environment and climate. However, knowledge on HULIS evolution during haze bloom-decay process is limited. Herein, PM2.5 samples were obtained during a winter haze event in Guangzhou, China, and the light absorption and molecular composition of HULIS were investigated by UV–Vis spectrophotometry and ultrahigh-resolution mass spectrometry. Compared with HULIS on clean days, the absorption coefficients (Abs365) of HULIS on haze days were significantly higher but the mass absorption efficiencies (MAE365) were relatively low, suggesting diverse and dynamic absorption properties of HULIS during haze episodes. The CHO and CHON compounds were the most abundant components in HULIS, followed by CHOS, CHONS, and CHN. Haze HULIS presented comparatively high molecular weight; a lower aromaticity index (AImod); and higher O/Cw, O/Nw, and O/Sw ratios, indicating that HULIS fractions undergo relatively high oxidation during haze days compared to clean days. Moreover, CHON and CHO compounds with high AImod were the major potential chromophores in HULIS and significantly contributed to HULIS light absorption. It is worth noting that the proportions of these chromophores decreased during haze events, mainly owing to their higher oxidation during haze episodes. Besides, accumulated contribution of organic compounds emitted from vehicles and formed from reactions of biogenic volatile organic compounds (bio-VOCs) also diluted light-absorbing compounds in haze HULIS. These findings help us to understand HULIS evolution during haze bloom-decay processes in the subtropic region of China.

Cohesive components in coal and their cohesive mechanism during pyrolysis

The cohesive components in coals and their detailed structure were investigated. The results show that the caking index of Linfen fat coal after extracting by benzene and tetrahydrofuran (THF) decreases from 89 to 43. Through analyzes of FT-IR and synchronous fluorescence spectrometry, anthanthrene is considered as the primary cohesive component to determine the cohesiveness of coal, and it is 42.4 wt% in the extract by THF from fat coal. Meanwhile, 1-naphthol, the secondary cohesive component to influence the cohesiveness of coal, is 22.8 wt% in the extract by benzene from fat coal. The cohesive phenomenon of coal has a positive correlation with the maximum aromaticity index (fa), and the cohesive phenomenon cannot be found during pyrolysis when the maximum fa of samples is smaller than 0.640, which are found from SEM images and XRD spectra of the carbonized samples. Moreover, the addition of anthanthrene makes Shenfu sub-bituminous coal produce cohesive phenomenon that coal particles connect together through the formation of a uniform surface. Based on these findings, a possible cohesive mechanism of coal was proposed.

Cover Feature: Quest for the Most Aromatic Pathway in Charged Expanded Porphyrins (Chem. Eur. J. 6/2023)

The aromaticity of charged expanded porphyrins turns out to be much more complex to study than that of their planar neutral analogues. In particular, identifying the most conjugated circuit is no longer straightforward. In addition to planarity, the protonation and deprotonation of porphyrinoids play an important role in determining their aromaticity. We have demonstrated that the largest charged porphyrins do not present a clear main conjugation pathway. Among the preferred aromatic indices, AVmin ends up being the most useful tool for recognizing the most aromatic path. We can relate the difficulty of finding the most conjugated path of a porphyrin to the number of pieces in a puzzle. Thus, the neutral state of the [36]octaphyrin is represented as a puzzle with few pieces; the protonated and deprotonated states are presented as puzzles with more pieces to indicate that they are more difficult to complete. More information can be found in the Research Article by M. Torrent-Sucarrat, E. Matito, M. Alonso, and co-workers (DOI: 10.1002/chem.202202264).

Predictive Modeling of Phase Behavior of Reservoir Fluids under Miscible Gas Injection Using the Peng-Robinson Equation of State and the Aromatic Ring Index.

Improved correlations among critical temperature, critical pressure, and acentric factor are developed for an extensive database of hydrocarbons. The correlations rely on measurements of molecular weight and refractive index at ambient conditions and utilize the concept of the aromatic ring index (ARI) recently developed by Abutaqiya et al. as a distinctive characterization factor for nonpolar hydrocarbons [Abutaqiya M. I. L.Aromatic Ring Index (ARI): A Characterization Factor for Nonpolar Hydrocarbons from Molecular Weight and Refractive Index. Energy Fuels2021, 35( (2), ), 1113-1119.]. The new correlations are then implemented for modeling the phase behavior of a variety of oils under miscible gas injection in a fully predictive manner using the Peng-Robinson equation of state (PR EOS). The results indicate that the proposed modeling framework yield accurate predictions for bubble pressure of oil/gas blends with an average absolute deviation of 6.4% for a wide variety of oils and injection gases including lean, rich, H2S, CO2, and N2. Additionally, an interesting crossover behavior in the phase envelope of live oils under CO2 injection is observed using PR EOS. This behavior has been previously reported in the literature for modeling results using PC-SAFT EOS and seems to be characteristic of CO2.

AROMATICITY OF AZA AROMATIC MOLECULES: PREDICTION FROM HÜCKEL THEORY WITH MODIFIED PARAMETERS

Hückel theory is a simple and powerful method for predicting the molecular orbital and the energy of conjugated molecules. However, the presence of nitrogen atoms in aza aromatic molecules alters the Coulomb and resonance integrals owing to the difference in electronegativity between nitrogen and carbon atoms. In this study, we focus on acridine and phenazine. Further correction is implemented based on the ring current model, thus revealing the change in resonance integral for the carbon–carbon bond along the bridge of the molecule. The Hamiltonian of the π–electron system in the Hückel method is solved using the HuLiS software. Various geometry-based aromaticity indices are used to obtain the aromaticity indices of the two non-equivalent rings. For further evaluation, the results for bond lengths are used to calculate the associated bond energy. Considering the carbon–hydrogen (CH) bonds, the total molecular energy is compared with the experimental heats of formation for a number of benzenoid hydrocarbons and aza aromatics, in addition to the two studied molecules. Finally, the correlation between the nitrogen atom on the aromaticity index and the ring energy content is evaluated to determine to which extent the Hückel model agrees with previous experimental and advanced computational studies.

A DFT study of the chemical bonding properties, aromaticity indexes and molecular docking study of some phenylureas herbicides

Herbicides have implied disastrous consequences towards the environment and human health. This practice urges scientists to investigate the physical, chemical and biological properties of these substances, hence avoiding the use of the most harmful pesticides. For this purpose, the molecular structure and chemical bonding properties of phenylurea herbicides namely: Fenuron (L1), Monuron (L2), Diuron (L3) and Chlorotoluron (L4), were calculated in water using density functional theory (DFT). The energy decomposition analysis (EDA) and the extended transition state natural orbitals for chemical Valence (ETS-NOCV) reveal the dominant ionic character in Carbon-Nitrogen bond between dimethylurea fragment and benzene ring. Besides, the interaction of these herbicides with the Human Serum Albumin (HSA) was undertaken by molecular modeling. The calculation of HOMA and FLU indexes indicate that the electronic delocalization is stronger in Diuron than the other compounds, mainly caused by the two chloro substituents effects on benzene. Good correlations are found between the calculated parameters such as structural parameters, Mulliken atomic charge, topological and bonding properties and aromaticity indexes. The Vinardo molecular docking results suggest that, the binding energies of the complexes formed between HSA target and investigated compounds have the following order: L3 (-27.57 kJ/mol) < L2 (-25.56 kJ/mol) < L4 (-24.94 kJ/mol) < L1 (-24.10 kJ/mol), which confirmed that the Fenuron is the less harmful option between the studied herbicides especially against HSA.

The electrophilic aromatic bromination of benzenes: mechanistic and regioselective insights from density functional theory.

The HBr-assisted electrophilic aromatic bromination of benzene, anisole and nitrobenzene was investigated using static DFT calculations in gas phase and implicit apolar (CCl4) and polar (acetonitrile) solvent models at the ωB97X-D/cc-pVTZ level of theory. The reaction profiles corresponding to either a direct substitution reaction or an addition-elimination process were constructed and insight into the preferred regioselectivity was provided using a combination of conceptual DFT reactivity indices, aromaticity indices, Wiberg bond indices and the non-covalent interaction index. Our results show that under the considered reaction conditions the bromination reaction preferentially occurs through an addition-elimination mechanism and without formation of a stable charged Wheland intermediate. The ortho/para directing effect of the electron-donating methoxy-group in anisole was ascribed to a synergy between strong electron delocalisation and attractive interactions. In contrast, the preferred meta-addition on nitrobenzene could not be traced back to any of these effects, nor to the intrinsic reactivity property of the reactant. In this case, an electrostatic clash between the ipso-carbon of the ring and the nitrogen atom resulting from the later nature of the rate-determining step, with respect to anisole, appeared to play a crucial role.

Rheological and Morphological Characterization of Modified Bitumen with Cup Lump Rubber

Pure bitumen is not suitable for heavy traffic loads; hence modifiers are used to improve the bitumen performance. Recently, cup lump rubber (CLR) has become a preferred modifier due to its outstanding performance and less cost. However, little is known about the interactions between CLR and bitumen. Thus, this study investigates the behavior of bitumen with CLR. Four percentages of CLR (2.5%, 5.0%, 7.5%, and 10.0% by weight of bitumen) were used to modify conventional 60/70 penetration grade bitumen. The modified bitumen was evaluated through different laboratory testing such as dynamic shear rheometer, rotational viscosity, softening point, bending beam rheometer, ductility, and elastic recovery. The testing results show that the addition of CLR increased the bitumen’s rutting resistance by 3 PG grades at high temperatures. At low pavement temperatures, the cup lump rubber modified bitumen (CMB) can withstand up to −34°C. Fourier Transform Infrared (FTIR) analysis shows that the Aromaticity index at 1600 cm-1 rose as the CLR percentage increased, indicating the formation of a binder with a compact structure. This is expected to improve the elasticity of bitumen through π – π interactions. Atomic Force Microscopy (AFM) results showed the Catana phase increased in size and quantity at 5.0% and 7.5% CLR content. While contact angle measurement revealed that the binders are hydrophobic and tend to repel the dropped water on the bitumen surface.

Pd and Pt metal atoms as electron donors in σ-hole bonded complexes.

Quantum calculations provide a systematic assessment of the ability of Group 10 transition metals M = Pd and Pt to act as an electron donor within the context of pnicogen, chalcogen, and halogen bonds. These M atoms are coordinated in a square planar geometry, attached to two N atoms of a modified phenanthrene unit, as well as two ligand atoms Cl, Br, or I. As the Lewis acid, a series of AFn molecules were chosen, which could form a pnicogen bond (A = P, As, Sb), chalcogen bond (A = S, Se, Te) or halogen bond (A = Cl, Br, I) with M. These noncovalent bonds are fairly strong, varying between 6 and 20 kcal mol-1, with the occupied dz2 orbital of M acting as the origin of charge transferred to the acid. Pt forms somewhat stronger bonds than Pd, and the bond strength rises with the size of the A atom of the acid. Within the context of smaller A atoms, the bond strength rises in the order pnicogen < chalcogen < halogen, but this distinction vanishes for the fifth-row A atoms. The nature of the ligand atoms on M has little bearing on the bond strength. Based on the Harmonic Oscillator Model of Aromaticity (HOMA) index, the ZB, YB and XB bonds were shown to have only a subtle effect on the ring electronic structures.

Distinct differences in surface-water dissolved organic matter between the East China Sea and Okinawa Trough: Source and hydrological effects

Cross-shelf transport plays an important role in marine carbon cycles. In this study, we examined the concentration and optical composition of dissolved organic matter (DOM) in 33 surface water samples collected along a transect from the East China Sea (ECS) to the Okinawa Trough (OT) in spring 2021. Compared to OT waters, ECS waters are characterized by higher dissolved organic carbon (DOC) concentration (111.55 ± 13.30 vs. 72.52 ± 5.01 μmol L−1), chromophoric DOM concentration (0.44 ± 0.15 vs. 0.12 ± 0.03 m−1 for a350), aromaticity (1.07 ± 0.11 vs. 0.64 ± 0.08 L mg−1C m−1 for SUVA254), and humification index (1.04 ± 0.25 vs. 0.58 ± 0.07). Fluorescence components C1, C3, and C4 displayed similar regional trends with the highest intensity in the inner shelf, followed by the outer shelf and then OT, whereas C2 had the highest intensity in the outer shelf, followed by the inner shelf and then OT. Comparison of the inner and outer ECS shelves revealed similar DOC concentrations, but different optical parameters (i.e., a350, S275–295, HIX, BIX, C1-C4 intensity). Our study suggests that: 1) active carbon cycling alters surface water DOM compositions in the ECS shelf, which is not reflected by total DOC concentrations, likely due to an offset effect between terrestrial DOM removal and marine DOM production; and 2) DOM is well mixed in the ECS shelf, but hardly passes across the OT owing to the strong barrier effect of the Kuroshio Current during the sampling season. Investigation of DOM biogeochemistry in other seasons and different water depth is necessary as the Changjiang Diluted Current and Kuroshio Current are weaker in winter and stronger in summer, respectively, which affects the spatial and temporal distribution of water DOM in the ECS-OT regions.

Aromaticity enhancement of cyclopentadiene in piperidine derivatives: a DFT study on combination of the anomeric effect and Schleyer hyperconjugative aromaticity

The cyclopentadiene (Cp) hyperconjugative aromaticity on anomeric carbon of piperidines was studied using DFT method. The aromaticity indices showed that Cp has considerably enhanced cyclic conjugation in comparison with unsubstituted Cp.

Cyclo[n]carbons and catenanes from different perspectives: disentangling the molecular thread.

All-carbon atomic rings, cyclo[n]carbons, have recently attracted vivid attention of experimentalists and theoreticians. Among them, cyclo[18]carbon is the most studied system. In this paper, we summarize and review various properties of cyclo[n]carbons, emphasising the aspects of their aromaticity/antiaromaticity. In the first part, the trends in bonding patterns and selected aromaticity indices with the increasing size of the rings are discussed. In the second part we explore the properties of catenane models based on interlocked cyclo[18]carbon rings from different perspectives and investigate their behaviour under the action of external force using computational experiments.

Spatiotemporal Variation of Riverine Dissolved Organic Matter Degradation Based on EEMs-PARAFAC: A Case Study of Shili River in Jiujiang, Jiangxi Province, China, as a Typical Demonstration City of the Yangtze River protection Strategy

This study investigated the spatio-temporal distribution of dissolved organic matter (DOM) composition and its sources before and after degradation in the Shili River watershed in Jiujiang (China). Spatio-temporal variation of riverine DOM water samples before and after five days of degradation in a simulated channel was characterized by spectral feature analysis using three-dimensional excitation-emission matrix fluorescence spectroscopy coupled with parallel factor analysis. Across all water samples (#1,#2 and #3) before and after degradation, a total of four fluorescent components in DOM were identified: C1, C2, C3, and C4. The aromaticity index (SUVA254) was negatively correlated with the C2 and C3 components and biological index (BIX) and freshness index (β:α), but it had little correlation with the humification index (HIX). The greater the aromaticity of DOM in water, the lower the proportion of recently produced DOM and its biological activity. The C3 component had a strong positive correlation with BIX, β:α, and C2. The results suggested that C2 and C3 were derived from the same substances. According to the fluorescence parameters, DOM was dominated by autochthonous contributions. The fluorescence intensity of DOM increased gradually along the direction of water flow. The increase of water temperature in spring and autumn enhanced the endogenous level of DOM. The levels and fluctuations of BIX and β:α in different seasons and different sampling points were basically consistent. DOC concentration does not fully represent the localized nature of the DOM. The analysis of some fluorescence parameters and light absorption parameters showed that the DOM source was more internal than terrestrial. This study reveals the composition, source and temporal and spatial characteristics of DOM in the Shili River Basin, which has theoretical guiding significance for water environment management.

A Benchmark Study of Aromaticity Indexes for Benzene, Pyridine, and the Diazines - II. Excited State Aromaticity.

In this work, one geometrical aromaticity index and four electron sharing indexes are benchmarked for their application in excited state aromaticity calculations. Two computationally feasible and reliable procedures are identified, namely, CAM-B3LYP/cc-pVTZ and ωB97X-D/cc-pVTZ. Topological effects on the first excited singlet and triplet electronic manifold were investigated, and the latter was in general found to display more aromatic character compared to the S1 surface. Besides, geometrical relaxation on each of the manifolds was observed to hamper the aromaticity, thereby resulting in more antiaromatic character. The relative order of excited state aromaticity within the studied molecules was noted to resemble the reversed version of the relative order of ground state aromaticity. Thereby, the following generalization was postulated: The more aromatic a molecule is in its ground state, the more antiaromatic it will be in its electronic first excited manifolds.

Effect of bio-asphalt as additive on macro and micro properties of TLA modified asphalt and its modification mechanism

Trinidad Lake Asphalt (TLA) modified asphalt has excellent high temperature performance, but its low temperature performance is poor, which limits its engineering application. But bio-asphalt presents relatively excellent low temperature performance. In this paper, TLA and Bio-asphalt were used as additives to prepare composite modified asphalt with excellent properties both at high and low temperatures. The micro modification mechanism of asphalt was studied by Fourier transform infrared spectroscopy (FTIR) and gel permeation chromatography (GPC). The macro mechanical behavior of asphalt binder was explored through routine physical property test and rheological property test. Finally, the mechanical properties of asphalt mixture were studied through the routine test of asphalt mixture, and the relationship between the macro and micro indexes of asphalt binder and the high and low temperature performance of asphalt mixture was established through grey correlation. The test shows that the mixing mode of TLA, bio-asphalt and base asphalt is physical blending. Modifiers affect the macro mechanical properties of asphalt by changing the distribution of asphalt components, the size of molecular weight, the interaction strength and arrangement of molecules. TLA improves the performance of asphalt binder at high temperature, but weakens the low-temperature performance. The low temperature performance of TLA modified asphalt was significantly improved by adding bio-asphalt at the cost of slightly reducing the high temperature performance. When the content of bio-asphalt is 9%–12%, the bio-asphalt/TLA modified asphalt and its mixture have better performance on high and low temperature properties than that of base asphalt. The micro indexes such as aromatic ring index and weight average molecular weight are good indicators of the high temperature performance of asphalt mixture. Creep rate (m), equivalent brittle point (T1.2) and stiffness modulus (S) can reflect the low-temperature performance of asphalt mixture.

Comprehensive understanding of DOM reactivity in anaerobic fermentation of persulfate-pretreated sewage sludge via FT-ICR mass spectrometry and reactomics analysis

Understanding the composition and reactivity of dissolved organic matter (DOM) at molecular level is vital for deciphering potential regulators or indicators relating to anaerobic process performance, though it was hardly achieved by traditional analyses. Here, the DOM composition, molecular reactivity and transformation in the enhanced sludge fermentation process were comprehensively elucidated using high-resolution mass spectrometry measurement, and data mining with machine learning and paired mass distance (PMD)-based reactomics. In the fermentation process for dewatered sludge, persulfate (PDS) pretreatment presented its highest performance in improving volatile fatty acids (VFAs) production with the increase from 2,711 mg/L to 3,869 mg/L, whereas its activation in the presence of Fe (as well as the hybrid of Fe and activated carbon) led to the decreased VFAs production performance. In addition to the conventional view of improved decomposition and solubilization of N-containing structures from sludge under the sole PDS pretreatment, the improved VFAs production was associated with the alternation of DOM molecular compositions such as humification generating molecules with high O/C, N/C, S/C and aromatic index (AImod). Machine learning was capable of predicting the DOM reactivity classes with 74–76 % accuracy and found that these molecular parameters in addition to nominal oxidation state of carbon (NOSC) were among the most important variables determining the generation or disappearance of bio-resistant molecules in the PDS pretreatment. The constructed PMD-based network suggested that highly connected molecular network with long path length and high diameter was in favor of VFAs production. Especially, -NH related transformation was found to be active under the enhanced fermentation process. Moreover, network topology analysis revealed that CHONS compounds (e.g., C13H27O8N1S1) can be the keystone molecules, suggesting that the presence of sulfur related molecules (e.g., cysteine-like compounds) should be paid more attention as potential regulators or indicators for controlling sludge fermentation performance. This study also proposed the non-targeted DOM molecular analysis and downstream data mining for extending our understanding of DOM transformation at molecular level.