Search Results (213)

Better understanding the controlling factors of shale oil quality including density and viscosity plays a key role in exploring these unconventional pay zones efficiently and profitably. The shale oil extracted from the middle Permian Lucaogou Formation (P₂l) of Santanghu Basin becomes denser and more viscous from the Tiaohu Sag to Malang Sag. It has been proven that oil quality is negatively correlated with saturated hydrocarbon content and positively correlated with aromatic/resin content. However, the underlying controls at the molecular levels are not yet clear. In order to reveal the fundamental controls, shale oil samples with varying density and viscosity were collected from these two sags, and molecular compositions of these samples were analyzed by using gas chromatography–mass spectrometry (GC–MS) for the saturated and aromatic hydrocarbons and electrospray ionization (ESI) Fourier transform ion cyclotron resonance mass spectrometry (FT–ICR MS) for heteroatom hydrocarbons in resin fraction. Thereafter, correlation analysis was performed between oil density and viscosity and geochemical parameters associated with saturated, aromatic and NSO-containing compounds. The experimental results indicate that the oil thermal maturity levels play a major role, since both density and viscosity present significant negative correlations (correlation coefficient > 0.5) with the maturity parameters of n-alkanes, terpanes, steranes and triaromatic steranes. Organic facies also play a partial role as indicated by the significant positive correlations between density and viscosity and the parameters of tricyclic terpanes, dibenzothiophene/phenanthrene, and methylated phenanthrenes. In resin fraction, density presents better correlations with acid compounds, including O_x (x = 5–9), N₁O_x (x = 0–2) and N₂O₃ species, and viscosity shows better correlations with basic N-containing compounds (N₁O₁, N₁O₃, and N₂O₁ species) and S-containing compounds (N₁S₁ and O₁S₁ species). This indicates that the cross-linking by acid oxygen-containing compounds and the intramolecular and intermolecular forces induced by basic N-containing compounds and sulfur-containing compounds play an important role in directing the P₂l shale oil quality. Moreover, the ratios of specific species with low-to-high double bond equivalents (DBEs) and the homologues with low molecular weight to high molecular weight both present significant negative correlations with density and saturated and aromatic maturity parameters. This highlights the effects of bond cleavage, cyclization and aromatization reactions with elevated thermal maturity in enhancing oil quality in the targeted pay zones. Most P₂l shale oil sources were deposited under the reducing lacustrine setting, containing mainly Type I/II kerogens. Shale oils from Tiaohu Sag are more matured than those from Malang Sag, which is supposed to be responsible for the better oil quality in Tiaohu Sag. This study provides the supporting evidence for regulating shale oil quality in the Santanghu Basin at the molecular levels, and should be helpful in identifying the sweet spots of shale oil plays in this area. Full article

Perilla frutescens(L.) Britt. (P. frutescens) is an important medicinal and aromatic plant, whose leaf color and chemotype strongly influence its medicinal quality and economic value. All the previously discovered perillene (PL)-type P. frutescens are double-sided green, and whether the PL-type trait is tightly linked with the green-leaf trait in genetics remains to be clarified. This study aimed to address this question and attempt to create purple-leaf PL-type germplasm through perillaldehyde (PA) × PL hybridization. Three parallel experiments were conducted using purple-leaf PA-type P. frutescens as male parents and green-leaf PL-type P. frutescens as female parents. Chemotypes were identified by gas chromatography (GC). Association analyses between leaf color and chemotype were performed in segregating F₂ populations. Genes involved in leaf color formation and PL biosynthesis were mapped onto the published Hoko-3 reference genome to provide genomic evidence for the genetic relationship between the two traits. All F₁ individuals were uniformly PA-type. The three F₂ populations exhibited distinct leaf color–chemotype association patterns: Z01 (n = 118) showed a strong association (Fisher’s exact p = 9.13 × 10⁻¹⁰; φ = 0.564), Z02 (n = 117) showed no detectable association (p = 0.9; φ = 0.012), and Z03 (n = 88) showed a moderate association (p = 0.00669; φ = 0.289). Importantly, purple-leaf PL-type recombinants were obtained in F₂ populations and stably maintained through subsequent generations (F₃–F₅), demonstrating that the PL-type trait is not tightly linked with the green-leaf trait in P. frutescens. Genomic mapping genes related to leaf color and PL biosynthesis are distributed across multiple chromosomes and usually present as multiple loci, which is consistent with the pattern of incomplete linkage. The PL-type trait is recessive and not genetically tightly linked to the green-leaf traits in P. frutescens. The successful creation of a purple-leaf PL-type germplasm breaks the historical phenotypic constraint and provides a novel material for further dissection of the molecular mechanisms regulating secondary metabolism and organ coloration in P. frutescens. Full article

The ultraviolet (UV) copolymers of two monomers, one methacrylic and the other vinyl monomer (styrene, S) were prepared. As methacrylic monomers, citronellyl methacrylate (CM) or geranyl methacrylate (GM) were used. The preparation was proven to contain high solvent- and chemical-resistant copolymers due to their cross-linked structure with the conversion degree of the double bonds above 0.92 for poly(citronellyl methacrylate)/polystyrene (PCM/PS) and above 0.85 for poly(geranyl methacrylate)/polystyrene (PGM/PS) copolymers. The obtained copolymers showed only one glass transition temperature (T_g). Depending on the structure and amount of the used methacrylic monomer, the T_g values were from 0.4 °C to −15.2 °C for PCM/PS copolymers and from −23.2 °C to −50.5 °C for PGM/PS copolymers. The thermogravimetric analysis (TG/DTG) showed a higher thermal stability for PCM/PS (148–187 °C) than for PGM/PS copolymers (119–159 °C) in inert and oxidative atmospheres. The simultaneous thermogravimetric analysis coupled with Fourier Transform Infrared spectroscopy (TG/FTIR) showed that the pyrolysis and oxidative decomposition of the tested copolymers took place according to the radical mechanism. This led to receiving a mixture of low molecular mass organic molecules containing saturated and unsaturated fragments, carbonyl groups, aromatic fragments as well as to CO, CO₂ and H₂O. This indicated the depolymerization process (inert) and further oxidation processes of the initially formed volatiles and/or residues in oxidative conditions. Full article

The synthesis of carbon dots (CDs) from coal represents a promising strategy for advancing both the efficient, low-carbon utilization of coal resources and the cost-effective production of CDs. To enable the controlled, high-quality conversion of CDs from coal, a comprehensive understanding of the relationship between the coal chemical structure and the properties of CDs is crucial. This study prepared CDs from nine kinds of coal using a chemical oxidation method, and the correlations between properties of coal-based carbon dots and the original materials were revealed. The results show that the luminescence sites of coal-derived CDs are mostly distributed around 435 nm or 500 nm, where the former one relates to the confined sp² domains and the latter one is associated with the defect structure. Coal with a volatile content of about 20–30% in the nine samples was found to produce higher CD yields, with a maximum mass yield of 19.96%, accompanied by stronger fluorescence intensity. During chemical oxidation processes, the unsaturated double bonds (C=C, C=O) and aliphatic chains firstly break, and then aromatic clusters are formed by dehydrocyclization between carbon crystallites, followed by the introduction of a C–O group. The growth of the C–O group in the CDs contributes to a stronger fluorescence property. Furthermore, strong correlations were found between the carbon skeleton structure of raw coal and photoluminescence characteristics of corresponding CDs, as reflected by Raman parameters A_D1/A_G, I_D1/I_G, and FWHM_D. The findings offer significant insights into the precise modulation and control of coal-based carbon dot structures. Full article

VOCs are significant precursors for the formation of O₃ and SOA, directly impacting human health. This study employs multiple approaches to analyzing atmospheric VOCs by focusing on OVOCs including aldehydes, ketones, and phenols, with a case study in Beijing, China. We analyzed the concentration levels and compositions of VOCs and their atmospheric activities, offering a new perspective on VOCs. This analysis was conducted through offline measurements of volatile phenols and carbonyl compounds, complemented by online VOC observations during the summer period of high O₃ levels. The total atmospheric VOCs concentration was found to be 51.29 ± 10.01 ppbv, with phenols contributing the most (38.87 ± 11.57%), followed by carbonyls (34.91 ± 6.85%), and aromatics (2.70 ± 1.03%, each compound is assigned to only one category based on its primary functional group, with no double counting). Carbonyls were the largest contributors to the OFP at 59.03 ± 14.69%, followed by phenols (19.94 ± 4.27%). The contribution of phenols to the SOAFP (43.37 ± 9.53%) and the L_OH (67.74 ± 16.72%) is dominant. Among all quantified VOC species, phenol and formaldehyde exhibited the highest species-level contributions to atmospheric reactivity metrics, including L_OH, OFP and SOAFP, owing to their combination of elevated concentrations and large kinetic or MIR coefficients. Using the PMF model for source analysis, six main sources of volatile organic compounds were identified. Solvent use and organic chemicals production were found to be the primary contributors, accounting for 31.76% of the total VOCs emissions, followed by diesel vehicle exhaust (17.80%) and biogenic sources (15.51%). This study introduces important OVOCs such as phenols, re-evaluates the importance of OVOCs and their role in atmospheric chemical processes, and provides new insights into atmospheric VOCs. These findings are crucial for developing effective air pollution control strategies and improving air quality. This study emphasizes the importance of OVOCs, especially aldehydes and phenols, in the mechanism of summer O₃ generation. Full article

To explore the aging mechanism of (Styrene Butadiene Styrene) and CR (Crumb Rubber) composite-modified asphalt in a multi-source environment, the characteristics of functional group changes in the infrared spectroscopy of SBS and CR modifiers as well as their single and composite modified asphalts under thermal, UV, and coupled aging were tested using Attenuated Total Reflection–Fourier Transform Infrared Spectroscopy (ATR-FTIR) technology. It was found that SBS and CR modifiers exhibited significant yellowing degradation after aging due to high-energy effects, causing abstraction of α-hydrogen from polybutadiene via oxidation, initiating radical chain reactions. The addition of SBS and CR to asphalt significantly increased the absorption peaks of 966 cm⁻¹ polybutadiene and 699 cm⁻¹ polystyrene. However, certain labile bonds in the modified asphalt, such as the C-H bond, C-C bond, and C=C double bond in polycyclic aromatic hydrocarbons, were easily broken to produce reactive free radicals under aging, which reacted chemically with other components to produce new sulfoxide and carbonyl groups. Overall, the aging reaction of the asphalt was a dual sequential oxidation process. Under normal temperature conditions in the early stage, a large number of sulfoxides were oxidized. In the later stage of the reaction, as the concentration and persistence of active free radicals increased, the oxidation reaction of the asphalt benzyl carbon also enhanced significantly, ultimately generating carbonyls. Full article

A strategy for constructing trifluoromethylated spiroisoxazolones has been developed. This approach relies on the 1,3-dipolar cycloaddition of CF₃-substituted nitrile imines, generated in situ from trifluoroacetyl hydrazonoyl bromides and K₂CO₃, with the exocyclic double bond of 4-benzylidene-3-methylisoxazol-5(4H)-ones. The reaction provides a series of trifluoromethylated spiro(isoxazolone-pyrazoline) derivatives in moderate to high yields (up to 93%). The protocol exhibits broad substrate compatibility with respect to aromatic substituents on both reaction partners. To the best of our knowledge, the introduction of a trifluoromethyl group at the 3-position of the pyrazoline ring via nitrile imine cycloaddition chemistry has not been previously reported. The resulting products incorporate a valuable CF₃-substituted pyrazoline pharmacophore spiro-fused to an isoxazolone core and may be of interest for medicinal chemistry programs. Full article

The multicomponent synthesis of a novel and highly symmetric polyheterocycle based on the pyrrolo[3,4-b]pyridin-5-one core incorporating the privileged tetrahydroisoquinoline moiety is described. The target compound was synthesized as an inseparable mixture of stereoisomers through a pseudo-repetitive Ugi–Zhu five-component reaction (PR-UZ-5CR) coupled to a double post-transformation sequence involving an intermolecular aza Diels–Alder cycloaddition, an intramolecular N-acylation, and a final tandem aromatization step. The product was prepared in 63% overall yield, and with an excellent atom economy of 85%, within a total reaction time of 85 min, and a temperature range from 25 to 65 °C. Structural elucidation and molecular mass confirmation were successfully achieved through NMR and FT-IR spectroscopy, and high-resolution mass spectrometry (HRMS), respectively. Full article

Protein and nucleic acid play central roles in biology and pharmaceuticals. Both share a similar architecture made of a backbone and side chains. Protein has a peptide backbone and various side chains, whereas nucleic acid has a phosphate backbone and aromatic side chains. However, they are significantly different in the chemical properties of the backbone and side chains. The protein backbone is uncharged, while nucleic acid backbone is negatively charged. The protein side chains comprise widely different chemical properties. On the other hand, the nucleic acid side chains comprise a uniform chemical property of aromatic bases. Such differences lead to fundamentally different folding, molecular interactions and co-solvent interactions, which are the focus of this review. In regular protein secondary structures, the peptide groups form polar hydrogen bonds, making the interior hydrophilic. The side chains of different chemical properties are exposed on the outside of the protein secondary structures and participate in molecular and co-solvent interactions. On the other hand, hydrophobic/aromatic nucleobase side chains are located inside the typical double helix or quadruplex structures. The charged phosphate groups of the nucleic acid backbone are located outside, participating in electrostatic interactions. The nucleobases are also involved in molecular interactions, when exposed in breaks, hairpins, kinks and loops. These structural differences between protein and nucleic acid confer different interactions with commonly used co-solvents, such as denaturants, organic solvents and polymers. Full article

The Berberis nummularia fruit is rich in polyphenols and which are associated with the inhibition of carbohydrate-digesting enzymes. However, the phytochemical compositions, antioxidant strength, and the ability of the fruits on the inhibition of α-amylase to control postprandial blood glucose remained elusive. In this study, therefore, different concentrations of ethanol were used in ultrasound processing at 70 °C for 1 h to obtain the crude polyphenol of B. nummularia fruit (CPB) and obtain the purified polyphenol (PPB) using AB-8 macroporous resin. After this, the polyphenolic constituents within PPB were identified using LC-MS/QTOF and investigated for anti-hyperglycemic properties by sucrose loading test. The results showed that the optimal extraction yield (44.32 ± 2.08%) of CPB was achieved with 30% ethanol and the PPB from CPB was reached at 71.88 ± 2.74%. A total of 30 polyphenols including 13 phenolic acids, 13 flavonoids, 3 benzaldehyde derivatives, and 1 aromatic acid were identified, in which the caffeic acid had the highest content (426.20 ± 0.18 ng/mg). The PPB displayed potent α-amylase inhibitory activity with an IC₅₀ value of 69.91 μg/mL and kinetic analysis via Lineweaver–Burk double reciprocal plots confirmed a non-competitive inhibition mechanism. Moreover, at an administration dose of 100 mg/kg body weight (BW), PPB significantly reduced blood glucose levels by 13.75 ± 0.87% and exerted a marked ameliorative effect on postprandial hyperglycemia in vivo. Therefore, these findings provide a foundation for considering PPB as a beneficial functional food ingredient and a potential dietary supplement for the management of postprandial hyperglycemia. Full article

Pea protein yogurt (PPY), as an alternative to traditional dairy yoghurt, has the advantages of being a green raw material, lactose cholesterol-free, and adaptable to the needs of lactose-intolerant people. PPY was prepared by fermenting a mixture of pea protein and water (1:10, w/v) supplemented with 5% fructose for 10 h after heat sterilisation. During fermentation, lactic acid bacteria metabolise pea protein to produce aldehydes and other aromatic compounds, imparting a unique sweet–sour balance and mellow flavour. However, issues such as weak gel formation and prominent soybean-like off-flavours severely restrict the development and consumer acceptance of PPY. In this study, five fermentation systems were systematically investigated to elucidate the fermentation mechanisms of pea yoghurt and explore effective methods for eliminating undesirable soy flavours. The results indicated that hydrophobic interactions and disulfide bonds are the predominant forces driving gel formation in PPY. Additionally, the protein content increased by 0.81 g/100 g following fermentation. A total of 43 volatile flavour compounds—including aldehydes, alcohols, acids, ketones, and furans—were identified, among which the concentrations of hexanal and 2-pentylfuran, known markers for soybean off-flavour, significantly decreased. Furthermore, high-temperature and high-pressure treatments (121 °C, 3 min) demonstrated superior effectiveness in reducing soybean-like flavours. Although the high-temperature and high-pressure treatment, double-enzyme hydrolysis, and flavour-masking methods operate through distinct mechanisms, their flavour profiles converged, displaying substantial deodorisation effects and synergistic interactions. These findings provide a theoretical basis and processing parameters for flavour modulation in PPY; however, further formulation optimisation is required to enhance its nutritional and textural properties. PPY shows promise as a potential alternative to conventional dairy products in the future. Full article

The aromaticity of small boron clusters remains under scrutiny due to persistent inconsistencies between magnetic and electronic descriptors. Here, we reexamine B₃⁻, B₃⁺, B₄, B₄²⁺, and B₄²⁻ using a multidimensional approach that integrates Adaptive Natural Density Partitioning, Electron Density of Delocalized Bonds, magnetically induced current density, and the z-component of the induced magnetic field. We introduce a model in which σ-aromaticity arises from two distinct delocalization topologies: a radial 2e⁻ σ-pathway and a tangential multicenter circuit formed by alternating filled and vacant sp² orbitals. This framework accounts for the evolution of aromaticity upon oxidation or reduction, preserving coherence between electronic structure and magnetic response. B₃⁻ features cooperative radial and tangential σ-delocalization, together with a delocalized 2e⁻ π-bond, yielding robust double aromaticity. B₃⁺ retains σ- and π-aromaticity, but only via a tangential 6e⁻ σ-framework, leading to a more compact delocalization and slightly attenuated ring currents. In B₄, the presence of a radial 2e⁻ σ-bond and a 4c–2e π-bond confers partial aromatic character, while the tangential 8e⁻ σ-framework satisfies the 4n rule and induces a paratropic current. In contrast, B₄²⁺ lacks the radial σ-component but retains a tangential 8e⁻ σ-circuit and a 2e⁻ 4c–2e π-bond, leading to a σ-antiaromatic and π-aromatic configuration. Finally, B₄²⁻, exhibits delocalized π- and σ-circuits, yielding consistent diatropic ring currents, which confirms its fully doubly aromatic nature. Altogether, this analysis underscores the importance of resolving σ-framework topology and demonstrates that, when radial and tangential contributions are correctly distinguished, Hückel’s rule remains a powerful tool for interpreting aromaticity in small boron rings. Full article

The current study focuses on a preliminary evaluation of the use of solid residues produced from the distillation of selected medicinal and aromatic plants (MAP) as fertilizers for alkaline soils. Specifically, the residues of hemp (Cannabis sativa L.), helichrysum (Helichrysum Italicum (Roth) G. Don), lavender (Lavandula angustifolia Mill.), oregano (Origanum vulgare L.), rosemary (Rosmarinus officinalis L.) and sage (Salvia officinalis L.) were added in an alkaline and calcareous soil at the rates of 0 (control), 1, 2, 4 and 8%, in three replications (treatments), and the treated soils were analyzed. The results showed that upon application of the residues, soil electrical conductivity (EC), organic C, total N and the C/N ratio significantly increased, especially at the 4 and 8% rates. The same was found for soil available P, K, B, Cu and Mn. The effects of the residues on soil pH, cation exchange capacity (CEC) and available Zn and Fe were rather inconclusive, whereas soil available N significantly decreased, which was somewhat unexpected. From the different application rates tested, it seems that all residues could improve soil fertility (except N?) when they were applied to soil at rates of 2% and above, without exceeding the 8% rate. The reasons for the latter statement are soil EC and available Mn: the doubling of EC upon application of the residues and the excessive increase in soil available Mn in treatments with 8% residues raise concerns of soil salinization and Mn phytotoxicity risks, respectively. This work provides the first step towards the potential agronomic use of solid residues from MAP distillation in alkaline soils. However, for the establishment of such a perspective, further research is needed in respect to the effect of residues on plant growth and soil properties, by means of at least pot experiments. Based on the results of the current study, the undesirable effect of residues on soil available N should be investigated in depth, since N is the most important essential element for plant growth, and possible risks of micronutrient phytotoxicities should also be studied. In addition, application rates between 2 and 4% should be studied extensively in order to recommend optimum application rates of residues to producers. Full article

The aromatic C₁₃ apocarotenoid β-ionone is a high-value natural-flavor and -fragrance compound derived from the oxidative cleavage of carotenoids. Carotenoid cleavage dioxygenases (CCDs) play a pivotal role in the biosynthesis of volatile apocarotenoids, particularly β-ionone. In this study, we report the identification, cloning, and functional characterization of two CCD1 homologs: OeCCD1 from Olea europaea and InCCD1 from Ipomoea nil. These two species, which, respectively, represent a woody perennial and a herbaceous annual, were selected to explore the potential functional divergence of CCD1 enzymes across different plant growth forms. These CCD1 genes were synthesized using codon optimization for Escherichia coli expression, followed by heterologous expression and purification using a GST-fusion system. In vitro assays confirmed that both enzymes cleave β-carotene at the 9,10 (9′,10′) double bond to yield β-ionone, but only OeCCD1 exhibits detectable activity on zeaxanthin; InCCD1 shows no in vitro cleavage of zeaxanthin. Kinetic characterization using β-apo-8′-carotenal as substrate revealed, for OeCCD1, a K_m of 0.82 mM, V_max of 2.30 U/mg (k_cat = 3.35 s⁻¹), and k_cat/K_m of 4.09 mM⁻¹·s⁻¹, whereas InCCD1 displayed K_m = 0.69 mM, V_max = 1.22 U/mg (k_cat = 1.82 s⁻¹), and k_cat/K_m = 2.64 mM⁻¹·s⁻¹. The optimization of expression parameters, as well as the systematic evaluation of temperature, pH, solvent, and metal ion effects, provided further insights into the stability and functional diversity within the plant CCD1 family. Overall, these findings offer promising enzymatic tools for the sustainable production of β-ionone and related apocarotenoids in engineered microbial cell factories. Full article

The SARS-CoV-2 main protease (Mpro), essential for viral replication, remains a prime target for antiviral drug design against COVID-19 and related coronaviruses. In this study, we present a systematic investigation into the molecular determinants of Mpro inhibition using an integrated approach combining large-scale data mining, cheminformatics, and quantum chemical calculations. A curated dataset comprising 963 high-resolution structures of Mpro–ligand complexes—348 covalent and 615 non-covalent inhibitors—was mined from the Protein Data Bank. Cheminformatics analysis revealed distinct physicochemical profiles for each inhibitor class: covalent inhibitors tend to exhibit higher hydrogen bonding capacity and sp³ character, while non-covalent inhibitors are enriched in aromatic rings and exhibit greater aromaticity and lipophilicity. A novel descriptor, Weighted Hydrogen Bond Count (WHBC), normalized for molecular size, revealed a notable inverse correlation with aromatic ring count, suggesting a compensatory relationship between hydrogen bonding and π-mediated interactions. To elucidate the energetic underpinnings of molecular recognition, 40 representative inhibitors (20 covalent, 20 non-covalent) were selected based on principal component analysis and aromatic ring content. Quantum mechanical calculations at the double-hybrid B2PLYP/def2-QZVP level quantified non-bonded interaction energies, revealing that covalent inhibitors derive binding strength primarily through hydrogen bonding (~63.8%), whereas non-covalent inhibitors depend predominantly on π–π stacking and CH–π interactions (~62.8%). Representative binding pocket analyses further substantiate these findings: the covalent inhibitor F2F-2020198-00X exhibited strong hydrogen bonds with residues such as Glu166 and His163, while the non-covalent inhibitor EDG-MED-10fcb19e-1 engaged in extensive π-mediated interactions with residues like His41, Met49, and Met165. The distinct interaction patterns led to the establishment of pharmacophore models, highlighting key recognition motifs for both covalent and non-covalent inhibitors. Our findings underscore the critical role of aromaticity and non-bonded π interactions in driving binding affinity, complementing or, in some cases, substituting for hydrogen bonding, and offer a robust framework for the rational design of next-generation Mpro inhibitors with improved selectivity and resistance profiles. Full article