Hydrocarbon Molecules Research Articles

Enhanced photocatalytic degradation of polycyclic aromatic hydrocarbon by graphitic carbonitride-nickel (g–C3N4–Ni) nanocomposite

The objective of the present study is to synthesize g-C3N4–Ni nanocomposites composed of graphitic carbon nitride and magnetic nickel nanoparticles for benzopyrene degradation, which is one of the most potent polycyclic aromatic hydrocarbons (PAH) molecules. The concocted g-C3N4–Ni nanocomposites contained confined nanospheres with a mean particle dimension of 22 nm. Batch adsorption studies revealed that a rise in adsorbent dosage elevates benzopyrene degradation percentage in both water and soil samples with respect to time. The increase in the benzopyrene concentration did not have much influence on the degradation efficiency, and hence, the minimal concentration of PAH molecule is essential for the effective adsorption by g-C3N4–Ni nanocomposites. The rise in pH tends to increase the degradation of Benzopyrene till 3 h of the incubation period, and beyond 3 h, the degradation percentage declines. With regard to the effect of light source, UV light has been shown to accelerate the degradation of benzopyrene by g-C3N4–Ni nanocomposites than sunlight. The adsorption kinetic and isotherm investigations have proven that the Pseudo-second order kinetic model and Freundlich isotherm model were appropriate for our study. Thus, the g-C3N4–Ni nanocomposites were found to be efficient as a photocatalyst for the adsorption of benzopyrene from environmental samples.

Aliphatics and Aromatics in the Universe: The Pre-JWST Era

The so-called “unidentified infrared emission” (UIE) features at 3.3, 6.2, 7.7, 8.6, and 11.3 μm ubiquitously seen in a wide variety of astrophysical regions are generally attributed to polycyclic aromatic hydrocarbon (PAH) molecules. Astronomical PAHs often have an aliphatic component (e.g., aliphatic sidegroups like methyl –CH3 may be attached as functional groups to PAHs) as revealed by the detection in many UIE sources of the aliphatic C–H stretching feature at 3.4 μm. With its unprecedented sensitivity and spatial resolution, and high spectral resolution, the James Webb Space Telescope (JWST) holds great promise for revolutionizing the studies of aliphatics and aromatics in the Universe. To facilitate analyzing JWST observations, we present a theoretical framework for determining the aliphatic fractions (η ali) of PAHs (the fractions of C atoms in aliphatic units) from the emission intensity ratios of the 3.4 μm aliphatic C–H feature to the 3.3 μm aromatic C–H feature. To demonstrate the effectiveness of this framework, we compile the 3.3 and 3.4 μm UIE data obtained in the pre-JWST era for an as-complete-as-possible sample, and then apply the framework to these pre-JWST data. We derive a median aliphatic fraction of 〈η ali〉 ≈ 5.4%, and find that the aliphatic fractions are the highest in protoplanetary nebulae illuminated by cool stars lacking ultraviolet radiation. Nevertheless, the “hardness” of stellar photons is not the only factor affecting the PAH aliphaticity, and other factors such as the starlight intensity may also play an important role.

Pd nanoparticles lubricant additive catalyze the construction of carbon-based tribofilm to reduce graphitization-induced wear of DLC films under boundary lubrication

To explore approaches of reducing graphitization-induced wear on the friction surface of DLC films under boundary lubrication to increase their service life, Pd nanoparticles (PdNPs) prepared by chemical reduction method were used as lubricant additive of DLC films and GCr15 ball under boundary lubrication. Tribotests, reactive force field molecular dynamics (ReaxFF MD) and surface characterization methods, such as SEM, XPS, Raman and FIB-TEM, were used to study the effects of PdNPs as lubricant additive on the graphitization-induced wear of DLC films and the effect mechanisms. The results show that, PdNPs lubricant additive can reduce the friction coefficient (COF) of the tribosystems, and more importantly, they can obviously increase the lifespan of DLC films. Characterization results indicate that PdNPs can promote the tribochemical reaction on the friction surface and catalyze the formation of carbon-based tribofilm on the friction surface, which significantly reduces the graphitization-induced wear of DLC films. ReaxFF MD studies show that PdNPs effectively catalyze the massive dehydrogenation and chain-breaking of base oil hydrocarbon molecules, providing the basis for the formation of carbon-based tribofilm. These results indicate that PdNPs are promising as effective additive to prolong the service life of DLC films under boundary lubrication.

Radiation assisted hydrophobization of jute fiber

AbstractHydrophobization of hydrophilic jute fiber, is of great importance as it can expand the applications of jute fiber in many fields. This work reports the hydrophobization of jute fiber by high‐energy radiation treatment which is an easy, single‐step, economical, and environment friendly method. Surface wettability of hydrophilic jute fiber is tuned by attaching long chain hydrocarbon molecules, namely butyl methacrylate, octyl acrylate and lauryl methacrylate, using gamma radiation. Lauryl methacrylate is found to be the most suitable agent among the molecules used for generating desired extent of hydrophobicity. Important reaction parameters, namely total dose, dose rate, monomer concentration, and solvent composition are optimized to achieve the desired degree of modification, for imparting hydrophobicity. Mechanical and thermal analysis reveals that there is no considerable damage to the base structure of fibers during modification. Scanning electron microscopy (SEM) is supporting evidence of the intactness of fiber after modification. The successful grafting of jute fiber has also been evidenced by SEM. This lauryl methacrylate modified jute can separate oily toxic liquids from aqueous media. The modified jute fiber may get enhanced applications in various fields.

Microstructural observations of clay-hosted pores in black shales: implications for porosity preservation and petrophysical variability

AbstractTypical unconventional gas/liquid plays of China were studied using field-emission/focused ion beam scanning electron microscopy (SEM) for clay mineralogy and microstructural development. The SEM microstructural investigations of clay-rich shale and mudstone reservoirs provided significant information about clay mineral type, size, distribution and aggregates, which allows for interpretations regarding porosity preservation and petrophysical variability. The major clay-hosted porosity types are interparticle clay pores, intraparticle clay pores and aggregate pores. Interparticle clay pores occur in open spaces of the clay aggregates and include four subtypes: (1) elongated pores, (2) packed pores, (3) jagged pores and (4) card-house pores. Intraparticle clay pores are present within clay particles and have mostly secondary origin. These pores are diagenesis dependent and are restricted to secondary illite particles during the transformation of clay minerals from smectite to illite. Intraparticle clay pores constitute only isolated porosity and could not contribute to hydrocarbon molecule storage and migration. Aggregate pores were predominantly encountered in association with organic–clay and pyrite–clay aggregates. In places, organic–pyrite–clay aggregates can also display polymerization, but they do not contribute significantly to overall porosity and permeability. Combining SEM morphological analyses with the software ImageJ is critical in clay microstructure and porosity analyses via semi-quantitative characterization of the 3D pore surface, 2D pore profile, pore quantity, pore size, areal porosity, etc. These visual and semi-quantitative results highlight the significance of jagged pores and pyrite–clay aggregate pores in shale gas/liquid reservoirs because they may be important facilitators of gas storage and transmission.

Hexa-Branched Nanographenes with Large Two-Photon Absorption.

The conventional approach toward molecules with large two-photon absorption (TPA) involves donor-acceptor conjugation. Herein we show a new strategy involving the use of hexa-branched nanographenes. We synthesized two hexa-branched nanographenes, one with six benzoaceanthrylene arms fused to the coronene core and the other with six pyrenyl arms fused to the coronene core. Neither of these hexa-branched nanographenes has a donor-acceptor structure, yet they exhibited high TPA values of 3.6 × 103 and 1.9 × 104 GM, respectively, which are the highest values recorded for heteroatom-free hydrocarbon molecules. Theoretical analysis suggests that the fused branched structures are responsible for the large TPA cross-section. These findings illustrate the importance of the topology of the fused conjugated skeleton in TPA and provide an alternative structural design toward large TPA.

(Invited) Optical Investigation of Single Nanographenes

Carbon based light emitters ranging from small organic molecules to carbon nanotubes have been subject of a great attention in the framework of diverse applications such as optoelectronics, bio-imaging, and quantum technologies. In this context, graphene quantum dots (GQD) whose size is between that of small polycyclic aromatic hydrocarbon molecules and of carbon nanotubes, have important assets. In particular the complete control of the structure allowed by their synthesis through bottom-up chemistry opens the way to a wide customization of their electronic, optical, and spin properties [1-3].The full benefit from these opportunities requires addressing GQD’s intrinsic photophysical properties. To do so, single molecule photoluminescence experiment is a powerful tool [4-6]. Nevertheless, until now, GQDs faced a problem of solubility that has complexified both the study of their intrinsic properties and their use for applications. In this presentation, we will report on the study of new structures that show a quasi-perfect solubility. We will show how this breakthrough allows us studying in depth their photophysics. Finally, we will see that the theoretical predictions of the evolution of the electronic properties of the GQDs with their structure are fully confirmed by the experiments.[1] M. G. Debije, J. Am. Chem. Soc. 2004, 126, 4641[2] X. Yan, X. Cui, and L.-s. Li, J. Am. Chem. Soc. 2010 132, 5944[3] A. Konishi et al, J. Am. Chem. Soc. 2010, 132, 11021[4] S. Zhao et al, Nature Communications, 2018, 9, 3470[5] T. Liu et al, Nanoscale, 14, 3826 – 3833 (2022)[6] T. Liu et al, Journal of Chemical Physics 156, 104302 (2022)[7] D. Medina-Lopez et al, in preparation

Deuterated Polycyclic Aromatic Hydrocarbons in the Interstellar Medium: The Aliphatic C–D Band Strengths

Abstract Deuterium (D) was exclusively generated in the Big Bang, and the standard Big Bang nucleosynthesis (BBN) model predicts a primordial abundance of D/H ≈ 26 parts per million (ppm). As the Galaxy evolves, D/H gradually decreases because of astration. The Galactic chemical evolution (GCE) model predicts a present-day abundance of D/H ≳ 20 ppm. However, observations of the local interstellar medium have revealed that the gas-phase interstellar D/H varies considerably from one region to another and has a median abundance of D/H ≈ 13 ppm, substantially lower than predicted from the BBN and GCE models. It has been suggested that the missing D atoms of D/H ≈ 7 ppm could have been locked up in deuterated polycyclic aromatic hydrocarbon (PAH) molecules. However, we have previously demonstrated that PAHs with aromatic C–D units are insufficient to account for the missing D. Here we explore if PAHs with aliphatic C–D units could be a reservoir of D. We perform quantum chemical computations of the vibrational spectra of superdeuterated PAHs (in which one D and one H share one C atom) and PAHs to which a D-substituted methyl group is attached, and derive the band strengths of the aliphatic C–D stretch (A 4.65). By applying the computationally derived A 4.65 to the observed aliphatic C–D emission at ∼4.6–4.8 μm, we find that PAHs with aliphatic C–D units could have tied up a substantial amount of D/H and marginally account for the missing D. The possible routes for generating PAHs with aliphatic C–D units are also discussed.

Application of Ion Mobility Spectrometry-Mass Spectrometry for Compositional Characterization and Fingerprinting of a Library of Diverse Crude Oil Samples.

Exposure characterization of crude oils, especially in time-sensitive circumstances such as spills and disasters, is a well-known analytical chemistry challenge. Gas chromatography-mass spectrometry is commonly used for "fingerprinting" and origin tracing in oil spills; however, this method is both time-consuming and lacks the resolving power to separate co-eluting compounds. Recent advances in methodologies to analyze petroleum substances using high-resolution analytical techniques have demonstrated both improved resolving power and higher throughput. One such method, ion mobility spectrometry-mass spectrometry (IMS-MS), is especially promising because it is both rapid and high-throughput, with the ability to discern among highly homologous hydrocarbon molecules. Previous applications of IMS-MS to crude oil analyses included a limited number of samples and did not provide detailed characterization of chemical constituents. We analyzed a diverse library of 195 crude oil samples using IMS-MS and applied a computational workflow to assign molecular formulas to individual features. The oils were from 12 groups based on geographical and geological origins: non-US (1 group), US onshore (3), and US Gulf of Mexico offshore (8). We hypothesized that information acquired through IMS-MS data would provide a more confident grouping and yield additional fingerprint information. Chemical composition data from IMS-MS was used for unsupervised hierarchical clustering, as well as machine learning-based supervised analysis to predict geographic and source rock categories for each sample; the latter also yielded several novel prospective biomarkers for fingerprinting of crude oils. We found that IMS-MS data have complementary advantages for fingerprinting and characterization of diverse crude oils and that proposed polycyclic aromatic hydrocarbon biomarkers can be used for rapid exposure characterization. Environ Toxicol Chem 2023;42:2336-2349. © 2023 The Authors. Environmental Toxicology and Chemistry published by Wiley Periodicals LLC on behalf of SETAC.

Polycyclic aromatic hydrocarbon molecules and the 2175Å interstellar extinction bump

ABSTRACT The exact nature of the 2175$\mathring{\rm A}$ extinction bump, the strongest spectroscopic absorption feature superimposed on the interstellar extinction curve, remains unknown ever since its discovery in 1965. Popular candidate carriers for the extinction bump include nano-sized graphitic grains and polycyclic aromatic hydrocarbon (PAH) molecules. To quantitatively evaluate PAHs as a possible carrier, we perform quantum chemical computations for the electronic transitions of 30 compact, pericondensed PAH molecules and their cations as well as anions with a wide range of sizes from 16 to 96 C atoms, and a mean size of 43 C atoms. It is found that a mixture of such PAHs, which individually exhibit sharp absorption features, show a smooth and broad absorption band that resembles the 2175$\mathring{\rm A}$ interstellar extinction bump. Arising from π* ← π transitions, the width and intensity of the absorption bump for otherwise randomly selected and uniformly weighted PAH mixtures, do not vary much with PAH sizes and charge states, whereas the position somewhat shifts to longer wavelengths as PAH size increases. While the computed bump position, with the computational uncertainty taken into account, appears to agree with that of the interstellar extinction bump, the computed width is considerably broader than the interstellar bump if the molecules are uniformly weighted. It appears that, to account for the observed bump width, one has to resort to PAH species of specific sizes and structures.

H2 formation via non-Born-Oppenheimer hydrogen migration in photoionized ethane

Neutral H2 formation via intramolecular hydrogen migration in hydrocarbon molecules plays a vital role in many chemical and biological processes. Here, employing cold target recoil ion momentum spectroscopy (COLTRIMS) and pump-probe technique, we find that the non-adiabatic coupling between the ground and excited ionic states of ethane through conical intersection leads to a significantly high yield of neutral H2 fragment. Based on the analysis of fingerprints that are sensitive to orbital symmetry and electronic state energies in the photoelectron momentum distributions, we tag the initial electronic population of both the ground and excited ionic states and determine the branching ratios of H2 formation channel from those two states. Incorporating theoretical simulation, we established the timescale of the H2 formation to be ~1300 fs. We provide a comprehensive characterization of H2 formation in ionic states of ethane mediated by conical intersection and reveals the significance of non-adiabatic coupling dynamics in the intramolecular hydrogen migration.

An atomistic model of aged asphalt guided by the oxidation chemistry of benzylic carbon with application to asphalt rejuvenated with a triglyceride

Waste cooking oil (WCO) shows promise for restoring physical properties of aged asphalt binder to enable pavement recycling. Its use as a rejuvenator lessens the environmental burden on land fills with its disposal. In this study, we report our initial development of an aged asphalt model and the computational investigation of the effect of triglycerides, the main component of WCO, on the viscosity, self-diffusion, and microstructural properties of aged asphalt at 1 atm and 404 K. The fundamental research question in this work involves understanding the underlying mechanism(s) by which WCO rejuvenates aged asphalt binder. A central feature of this aged asphalt model is consideration of oxidation chemistry and reported functional group concentrations since properties like viscosity are known to be related to the amounts of moieties such as ketones and sulfoxides. Model oxidation compounds include proposed representative asphalt structures based on Peterson’s dual reaction pathways, leading to polycyclic aromatic hydrocarbon molecules resulting from fast phase aromatization and multiple species from a slow phase degradation of benzylic hydroperoxide intermediates. The new model takes into account the observed product distribution of aryl alcohols and aryl ketones based on findings for cumene oxidation in the literature. Other oxygen-containing functional groups, such as anhydrides, carboxylic acids, and polynuclear aromatics, have been incorporated to account for the critical physical characteristics of aged asphalt. By extending the molecular basis set of asphalt components, we can now construct more realistic asphalt models to represent varying SARA (Saturates, Aromatics, Resins, Asphaltents) content, different oxidation levels and functional group composition. Virtual representations of the molecules in the basis set were created and molecular dynamics simulations of the aged asphalt model conducted. Results with aged asphalt basis set provided good agreement with reported physical properties. With the developed aged asphalt model, our molecular dynamics simulations reveal that triglyceride (tristearin) has preferential interactions with asphaltene molecules. On addition of 10 wt% triglyceride to aged asphalt, the asphaltene-asphaltene interaction was most significantly affected. The radial distribution functional analysis revealed that the asphaltene-asphaltene nearest neighbor distance increased from 4.0 Å to 7.5 Å. Thus, adding triglyceride to aged asphalt helps to reduce the aggregation of asphalt components and as such promotes a decrease in viscosity of the aged asphalt, from 83 cP to 69 cP. In addition, the asphaltene components have larger self-diffusion coefficients upon the addition of triglyceride, changing from 3.57 × 10−8 cm2/s in the aged asphalt to 1.41 × 10−7 cm2/s in the triglyceride/aged asphalt mixture. Those findings are consistent with the observed effectiveness of utilizing waste cooking oil to rejuvenate aged asphalt.

A Microporous Zn(bdc)(ted)0.5 with Super High Ethane Uptake for Efficient Selective Adsorption and Separation of Light Hydrocarbons.

Separating light hydrocarbons (C2H6, C3H8, and C4H10) from CH4 is challenging but important for natural gas upgrading. A microporous metal-organic framework, Zn(bdc)(ted)0.5, based on terephthalic acid (bdc) and 1,4-diazabicyclo[2.2.2]octane (ted) ligands, is synthesized and characterized through various techniques, including powder X-ray diffraction (PXRD), scanning electron microscopy (SEM), thermogravimetric analysis (TGA), and porosity analysis. The adsorption isotherms of light hydrocarbons on the material are measured and the isosteric adsorption heats of CH4, C2H6, C3H8, and C4H10 are calculated. The prediction of C2-4/C1 adsorption selectivities is accomplished using ideal adsorbed solution theory (IAST). The results indicate that the material exhibits exceptional characteristics, including a Brunauer-Emmett-Teller (BET) surface area of 1904 m2/g and a pore volume of 0.73 cm3/g. Notably, the material demonstrates remarkable C2H6 adsorption capacities (4.9 mmol/g), while CH4 uptake remains minimal at 0.4 mmol/g at 298 K and 100 kPa. These findings surpass those of most reported MOFs, highlighting the material's outstanding performance. The isosteric adsorption heats of C2H6, C3H8, and C4H10 on the Zn(bdc)(ted)0.5 are higher than CH4, suggesting a stronger interaction between C2H6, C3H8, and C4H10 molecules and Zn(bdc)(ted)0.5. The molecular simulation reveals that Zn(bdc)(ted)0.5 prefers to adsorb hydrocarbon molecules with richer C-H bonds and larger polarizability, which results in a stronger dispersion force generated by an adsorbent-adsorbate induced polarization effect. Therefore, the selectivity of C4H10/CH4 is up to 180 at 100 kPa, C3H8/CH4 selectivity is 67, and the selectivity of C2H6/CH4 is 13, showing a great potential for separating C2-4 over methane.

Interfacial Rheological and Emulsion Properties of Self-Assembled Cyclodextrin-Oil Inclusion Complexes.

To investigate the effect of the molecular size of alkanes and the cavity size of cyclodextrins (CDs) on the formation of interfacial host-guest inclusion complexes, the interfacial tension (IFT) of CD (α-CD, β-CD, γ-CD) solutions against oils (hexadecane, dodecylbenzene) was determined by interfacial dilational rheology measurements. The results show that the "space compatibility" between CDs and oil molecules is crucial for the formation of interface host-guest inclusion complexes. Hexadecane with a smaller molecular size can form host-guest inclusion complexes with small cavities of α-CD and β-CD, dodecylbenzene with a larger molecular size can form interfacial aggregates with the medium-sized cavity of β-CD easily, and the polycyclic aromatic hydrocarbon molecules in kerosene can form inclusion complexes with the large cavity of γ-CD. The formation of interfacial inclusion complexes leads to lower IFT values, higher interfacial dilational modulus, nonlinear IFT responses to the interface area oscillating, and skin-like films at the oil-water interface. What's more, the phase behavior of Pickering emulsions formed by CDs with different oils is explored, and the phenomena in alkane-CD emulsions are in line with the results in dilatation rheology. The interfacial active host-guest structure in the kerosene-γ-CD system improves the stability of the Pickering emulsion, which results in smaller emulsion droplets. This unique space compatibility characteristic is of great significance for the application of CDs in selective host-guest recognition, sensors, enhanced oil recovery, food industries, and local drug delivery.

Synthesis of 1-(2,2-Dimethylpropyl)-Cyclopropene (1-DCP) as an Ethylene Antagonist.

Ethylene is a gaseous hydrocarbon molecule known as a plant hormone that promotes fruit ripening and senescence. Efficiently controlling ethylene is a central key to maintaining the quality of agricultural products. The current study uncovered a synthetic method for 1-(2,2-dimethylpropyl)-cyclopropene (1-DCP) as a cyclopropene derivative to inhibit ethylene action in fruit ripening and senescence. We synthesized 1-DCP using α-diisobutylene through a two-step process, including allylic chlorination by hypochlorite and HCl, followed by α-elimination of the allylic chloride using a strong base, lithium diethylamide. GC-MS and NMR analyses demonstrated that 1-DCP was synthesized efficiently with 35% yield and 95% purity. When treated as an aqueous emulsion on plants, including persimmon and banana fruits, 1 mM 1-DCP showed effective inhibition of ethylene action by delaying the flesh softening and peel degreening, which are representative phenomena of fruit ripening and senescence induced by ethylene. Our data demonstrated that 1-DCP could be synthesized and used as a sprayable ethylene antagonist for pre- or post-harvest growth regulation in plants and fruits.

The effect of electric field on the pyrolysis of transformer insulation oil–paper based on molecular dynamics

The regular operation of transformers is significantly impacted by the insulation effectiveness of the transformer insulation oil–paper. In order to explore the mechanism of the influence of an electric field on the thermal decomposition performance of insulating oil–paper, this paper simulated the process of electrothermal coupling decomposition of insulating oil–paper from the micro-level based on molecular dynamics. It was determined that the insulating oil is made up of three 16-carbon hydrocarbon molecules, while the insulating paper is made up of 30 fibrous disaccharide molecules. Using the molecular dynamics simulation approach, the pyrolysis of the insulating oil and insulating paper under various electric field strengths was simulated, and the lysis of reactants and the distribution of products were statistically examined. This paper also studied how the electric field affected the microscopic process of the insulating oil–paper pyrolysis. The findings demonstrate that under the influence of electrothermal coupling, the big molecules of the insulating oil and insulating paper are pyrolyzed to produce a variety of tiny molecules. For the insulating oil, it is easily subject to electron displacement polarization under the influence of an external electric field since it contains non-polar molecules, especially impacted by an electric field of 100 V/m. For the insulating paper, its polar nature, on the other hand, makes itself a good candidate for guiding polarization when exposed to an external electric field. So, the greater the electric field strength is, the greater the impact on the thermal decomposition of the insulating paper is.

Exciplex luminescence of difluoroboron meta- and para-Nitrodibenzoylmethanates in solutions and polymer matrix

Molecular systems with intense exciplex luminescence are promising for the creation of OLEDs and light-transforming materials. The luminescent properties of difluoroboron meta- and para-nitrodibenzoylmethanates (1 and 2) were studied by the steady-state and time-resolved luminescence spectroscopy methods and quantum chemistry simulation. The influence of the position of the nitro group on the spectral properties of the complexes was revealed. The nitro group withdraws the electron density upon photoexcitation in the para-isomer in contrast to the meta-isomer. The bond order of the CC bond between the phenyl and chelate rings decreases in the excited relaxed state of 2, which leads to rotation of the substituent and a low quantum yield. Formation of exciplexes of 1 and 2 in benzene, toluene and polystyrene was found. The formation of the ground and excited-state electron donor–acceptor complexes based on difluoroboron nitrodibenzoylmethanates and benzene was revealed. The TDDFT method showed that the complexes are characterized by the presence of short contacts between the fluorine atom of the dye molecule and the hydrogen atoms of the aromatic hydrocarbon molecule. These contacts shorten during the transition from the ground state to the excited state. Polymeric compositions based on polystyrene (PS) and poly(methyl methacrylate) (PMMA) doped with 1 and 2 were obtained. The luminescence intensity of dyes 1 and 2 increases during the transition from PMMA to PS. A significant bathochromic shift of the luminescence maximum of 1 is observed, which is associated with the formation of exciplexes and triplexes. The obtained polymeric materials are promising for the development of optical smart materials.

Effects of strong electric field and solvation on the excitation process of mineral oil molecules

Studying the excitation process of mineral oil molecules under the influence of electric fields and different environments is crucial for understanding the development of insulating oil streamer discharge at the atomic scale. In this paper, based on density functional theory, quantitative characteristic descriptors, hole-electron distribution, and transition density matrix (TDM) analysis, the excitation energies of the first five excited states are used to analyse the excitation process of mineral oil molecules under various conditions. The results obtained under four different electric field strengths (0, 0.0001 a.u., 0.001 a.u. and 0.01 a.u.) and three different environments (vacuum, mineral oil, and natural ester) are compared. The results show that for electric field strengths ranging from 0 to 0.001 a.u., the excitation types of the three mineral oil molecules are localized excitations. However, when the electric field intensity reaches 0.01 a.u., the excitation type of mineral oil molecules changes to charge transfer excitation due to the strong electric field. There are significant differences in the positions of holes and electrons in the excitation processes of the mineral oil molecules under different conditions. While the excitation process of chain hydrocarbon molecules under vacuum and in solution exhibits some differences, the excitation processes of dicycloalkanes and aromatic hydrocarbons are not affected by environmental factors. The electronic transitions in the excitation process of chain hydrocarbons and dicycloalkanes are sigma->sigma* transition processes, whereas in aromatic hydrocarbons, it is primarily pi->pi* transition processes. Compared to pi orbitals, sigma orbitals are lower energy empty orbitals, and sigma* orbitals are higher energy empty orbitals. As a result, the excitation energies of the chain hydrocarbons and dicycloalkanes are higher than that of aromatic hydrocarbons. Furthermore, a strong electric field changes the excitation type of mineral oil molecules, accompanied by a significant decrease in their excitation energy. The selection of insulating oil molecules, whose excitation process is sigma->sigma* or modifying the transition mode of electrons in the excitation process through doping and modification, is an important approach to improve the excitation energy of insulating oil. The findings of this research have the potential to enhance our understanding of the microscopic mechanisms that influence the development of streamer discharge in liquid insulating materials.

A New Pressure-Based Modeling Approach for Early Leak Detection in Gas Processing Plants Using Machine Learning

Natural gas is composed mostly of methane, the simplest hydrocarbon molecule, with only one carbon atom. But most gas at the wellhead contains other hydrocarbon molecules known as Natural Gas Liquids (NGL). Heavier gaseous hydrocarbons such as propane (C3H8), normal butane (n-C4H10), isobutane (i- C4H10) and pentanes, may also be processed in gas plants and exported as Liquified Natural Gas (LNG). During operational services in gas plant from inlet to outlet piping, gas leaks tend to occur undetected at some points in the facility. Apart from loss of gas resources, leaks and venting at natural gas processing plants release other pollutants besides methane (e.g., benzene, hexane, hydrogen sulfide) that can threaten air quality and public health. Hence, the need for early detection of gas leaks by using appropriate Machine Learning (ML) models. Insight from existing general flow equations was used to develop a new modelling approach for Machine Learning, in a test case: Gas Plant JK – 52. Input gas pressure data is calibrated and evaluated for consistency in real-time. The data is then corrected for lag-time and used to compute tolerance. Indicated time of alarm is checked against events such as residual gas, supply, pumping, etc. Where alarm is eventless, leak is suspected and eventually confirmed, suggesting that action should be taken to mitigate against the leakage. Following the input of a split training dataset, different types of regressions were used for the machine learning before automating the system for real-time evaluation and detection. Linear regression provided a 39% test accuracy, which was considered too low. This led to the use of random forest regression, which provided a 95% test accuracy and was considered excellent. It is hoped that with continuing data acquisition in gas plants employing this algorithm, further modelling will become more predictive as machine learns from experience.

Synthesis of Stable Neutral Homoaromatic Hydrocarbons

AbstractWe report the synthesis of a variety of stable neutral homoaromatic molecules. The homoaromatic character is supported by bond length analysis (from crystal structure analysis data) and spectroscopic characteristics in NMR experiments. The influence of substitution on these homoannulenes is investigated and their reactivity with electrophiles is shown. First approaches to further functionalization via cross-coupling are demonstrated. The present work lays out a general approach to stable neutral homoaromatic hydrocarbon molecules.