Search Results (634)

This study aims to investigate the tip resistance mechanism of open-ended steel pipe piles under partially plugged conditions by decomposing the load-sharing contribution of the ring zone and the internal soil core. A virtual static loading test was performed using the two-dimensional discrete element method (2D-DEM). Note that the findings of this study were obtained within the range of the 2D-DEM analysis conditions and do not intend to directly reproduce the three-dimensional arching mechanism or to establish equivalence between 2D and 3D responses. Quasi-static conditions were ensured by identifying loading parameters such that the energy residual remained ≤5% during driving, rest, and static loading phases, and the sensitivity criterion |Δq_b|/q_b ≤ 3% was satisfied when the loading rate was halved or doubled. The primary evaluation range of static loading was set to s/D = 0.1 (10% D), corresponding to the displacement criterion for confirming the tip resistance in the Japanese design specifications for highway bridges. For reference, the post-peak mechanism was additionally tracked up to s/D = 0.2 (20% D). Within a fixed evaluation window located immediately beneath the pile tip, high-contact-force (HCF) points were binarized using the threshold τ = μ + σ, and their occupancy ratio φ and normalized force intensity I* were calculated separately for the ring and core regions. A density-based contribution index (“K_{-density share}”) was defined by combining “strength × area” and normalizing by the geometric width. The results suggest that, for the sand conditions and particle-scale ratios examined (D/d_50 = 25–100), the ring zone tends to carry on the order of 85–90% of the tip resistance within the observed cases up to the ultimate state. Even at high plugging ratios (CRs), the internal soil core gradually increases its occupancy and intensity with settlement; however, high-contact-force struts beneath the ring remain active, and it is suggested that the ring-dominant load-transfer mechanism is generally preserved. In the post-peak plastic regime, the K_{-density share} remains around 60%, indicating that the internal core plays a secondary, confining role rather than becoming dominant. These findings suggest that the conventional plug/unplug classification based on PLR can be supplemented by a combined use of plugging ratio CR (a kinematic indicator) and the ring contribution index (K_{-density share}), potentially enabling a continuous interpretation of plugged and unplugged behaviors and contributing to the establishment of a design backbone for tip resistance evaluation. Calibration of design coefficients, scale regression, and mapping to practical indices such as N-values will be addressed in part II of this study. (Note: “Contribution” in this study refers to the HCF-based density contribution index K_{-density share}, not the reaction–force ratio.) Full article

Nucleophilic ring-opening of bis(oxiranes), containing several reactive centers, can be used to elaborate straightforward atom-economy and stereoselective approaches to polyfunctionalized compounds. In the present work, ring-opening of cis- and trans-diastereomers of a spirocyclic bis(oxirane), containing a cyclooctane core (namely, 1,8-dioxadispiro[2.3.2.3]dodecane), upon treatment with various amines, was studied. Trans-isomer afforded aminoalcohols with 9-oxabicyclo[3.3.1]nonane moiety, formed via domino-process, including opening of an oxirane ring followed by intramolecular cyclization. Ring-opening of cis-isomer gave aminosubstituted cis-cyclooctane-1,5-diols, derived from independent reaction of two oxirane moieties. Activation of oxirane rings by the addition of LiClO₄, acting as a Lewis acid, allowed the involvement of a number of primary and secondary aliphatic amines as well as aniline derivatives in the reaction. Scope and limitations of the reaction were studied and a series of aminoalcohols with a 9-oxabicyclo[3.3.1]nonane core and symmetric diaminodiols with a cyclooctane core were obtained. Full article

In this study, the advanced oxidation system of peroxymonosulfate (PMS) was activated by molybdenite supported on biochar (Molybdenite@BC), and the degradation efficiency, influencing factors and degradation mechanism of sulfamethoxazole (SMX) were explored through experiments. Molybdenite@BC, a composite material used in the study, was prepared by pyrolysis at high temperature. The optimum pyrolysis temperature was 700 °C, and the mass ratio of molybdenite to biochar (BC) was 1:3. By changing dosage of Molybdenite@BC, pH value, initial concentration of PMS, and the types and concentration of inorganic anions, the effects of various factors on SMX degradation were systematically studied. The optimum reaction conditions of the Molybdenite@BC/PMS process were as follows: Molybdenite@BC dosage was 100 mg/L, PMS concentration was 0.2 mM, pH value was 6.9 ± 0.2, and initial SMX concentration was 6 mg/L. Under these conditions, the degradation rate of SMX was 97.87% after 60 min and 99.06% after 120 min. The material characterization analysis showed that Molybdenite@BC had a porous structure and rich active sites, which was beneficial to the degradation of pollutants. After the composite material was used, the peaks of MoO₂ and MoS₂ became weaker, which indicated that there was some loss of molybdenum from the material structure. Electron paramagnetic resonance (EPR) and radical quenching experiments revealed that Molybdenite@BC effectively catalyzed PMS to generate various reactive oxygen radicals and non-free radicals, including singlet oxygen (¹O₂), hydroxyl radical (^•OH), sulfate radical (SO₄^•−) and superoxide radical (^•O₂⁻). ¹O₂ played a leading role in the degradation of SMX, while ^•OH and SO₄^•− had little influence. The intermediate products of the degradation of SMX in Molybdenite@BC/PMS system were analyzed by liquid chromatography–tandem mass spectrometry (LC–MS). The results showed that there were nine main intermediate products in the process of degradation, and the overall toxicity tended to decrease during the degradation of SMX. The degradation path analysis showed that with the gradual ring opening and bond breaking of SMX, small molecular compounds were generated, which were finally mineralized into H₂O, CO₂, CO₃²⁻, H₂SO₄ and other substances. The research results confirmed that the Molybdenite@BC/PMS process provided a feasible new method for the degradation of SMX in water. Full article

Agricultural biomass has potential as a renewable and versatile carbon feedstock for developing eco-friendly and biodegradable polymers capable of replacing conventional petrochemical plastics. To address the growing environmental concerns associated with plastic waste and carbon emissions, lignocellulosic residues, edible crop by-products, and algal biomass were utilized as sustainable raw materials. These biomasses provided carbohydrate-, lipid-, and lignin-rich fractions that were deconstructed through optimised physical, chemical, and enzymatic pretreatments to yield fermentable intermediates, such as reducing sugars, organic acids, and fatty acids. The intermediates were subsequently converted through tailored microbial fermentation processes into biopolymer precursors, primarily polyhydroxyalkanoates (PHAs) and lactate-based monomers. The resulting monomers underwent polymerization via polycondensation and ring-opening reactions to produce high-performance biodegradable plastics with tunable structural and mechanical properties. Additionally, the direct extraction and modification of naturally occurring polymers, such as starch, cellulose, and lignin, were explored to develop blended and functionalized bioplastic formulations. Comparative evaluation revealed that these biomass-derived polymers possess favourable physical strength, thermal stability, and biodegradability under composting conditions. Life-cycle evaluation further indicated a significant reduction in greenhouse gas emissions and improved carbon recycling compared to fossil-derived counterparts. The study demonstrates that integrating agricultural residues into bioplastic production not only enhances waste valorization and rural bioeconomy but also supports sustainable material innovation for packaging, farming, and consumer goods industries. These findings position agriculture-based biodegradable polymers as a critical component of circular bioeconomy strategies, contributing to reduced plastic pollution and improved environmental sustainability. Full article

Haloketoesters are synthetic intermediates in various cyclization reactions that facilitate the production of biologically active compounds. Nonetheless, the selective synthesis of dihaloketoesters and trihaloketoesters, which are expected to be highly versatile, presents significant challenges. In this study, we designed a new synthetic approach that selectively and efficiently produces haloketoesters through the halogenative C–C bond cleavage and ring-opening reactions of cyclic 1,3-diketones. This convenient method enables the direct synthesis of di- and trichloro-functionalized ketoesters from 1,3-cyclohexadiones under mild conditions. Na₂HPO₄, employed as a buffer salt, proved to be effective in facilitating the alcoholytic ring-opening reaction of 2,2-dichloro-1,3-cyclohexadiones, which were generated as synthetic intermediates. Full article

The ruthenium-catalysed silylative coupling (SC) reaction is a useful method for obtaining selectively functionalised organosilicon compounds, which have a wide range of applications in organometallic and organic chemistry. It is possible to prepare such compounds with norbornene matrices, which can be used for ring-opening metathesis polymerisation (ROMP) in the synthesis of linear-type polymers. Herein, we present a method for the synthesis of the aforementioned matrices by a condensation reaction between diol and vinylphenylboronic acids. Furthermore, these compounds were subsequently modified by SC reaction and polymerised by ROMP. To assess the possibility of using styryl-based silyl-derived monomers as building blocks in further organic transformations, the process of bromodesilylation was also investigated. We would also like to perform a comparative study on the selectivity of hydrosilylation and silylative coupling processes in the case of discovered materials. Full article

This study investigates the influence of various parameters on the synthesis of oligosiloxanes with degrees of polymerization below 15. The work provides insights into methods for synthesizing oligosiloxanes with precisely controlled molecular weight and degrees of polymerization. Low-molecular-weight polysiloxanes with well-defined molecular characteristics have attracted attention due to their versatile functional properties and potential applications. Although some studies have explored the control of polysiloxane molecular weights, precise regulation of oligosiloxane molecular weight has been rarely investigated. This study aims to establish optimized reaction conditions for the synthesis of oligosiloxanes with precisely controlled molecular weights. The results reveal that the molecular weight of oligosiloxanes can be effectively tuned by adjusting the molar ratio between the promoter and initiator, the initiator and cyclotrisiloxane (D₃), as well as by varying the lithium type and solvent composition in the ring-opening polymerization of D₃. These findings provide valuable guidance for tailoring oligosiloxane properties and expanding their potential applications in advanced materials. Full article

This paper demonstrates the successful synthesis of novel hybrid heterogeneous catalysts for the sustainable conversion of CO₂ into cyclic organic carbonates (COCs). The nanocat-alysts have been fabricated by encapsulating pre-formed ultra-small gold nanostructures into a nascent zinc-coordination polymer (ZnCP) framework formed from two organic building blocks, 2,4-naphthalenedicarboxylic acid (1,4-NDC) and 5-amino-1H-tetrazole (5-Atz), which serves as a nitrogen-rich ligand. Applying the fabricated catalysts in the synthesis of COCs yields high yields (up to 97%) and high selectivity (up to 100%), with exceptionally high turnover frequencies (TOFs) (up to 408 h⁻¹). The catalytic process can be carried out under mild conditions (80 °C, 1.5 MPa CO₂) and without the use of solvents. Nitrogen-rich ligand molecules in the structure of ZnCPs enhance catalytic performance thanks to additional nucleophilic centres, which are effective in the epoxides’ ring-opening process. The hybrid catalysts with encapsulated gold nanostructures, which modify the liquid–gas interface between epoxide and CO₂, give significantly higher yields and TOFs for less active epoxides. The designed hybrid nanocatalysts exhibit superior stability under the studied reaction conditions and can be reused without loss of activity. The developed coordination polymers are constructed from green components, and green chemistry principles are applied to prepare these catalytic materials. Full article

Azaoxyallyl cations, as novel and versatile three-atom components, have been widely utilized in cycloaddition reactions, with the competition between O- and N-cyclization pathways remaining a key research focus. This study investigates the mechanism and site selectivity of (3+2) cycloaddition between azaoxyallyl cations and 1,2-benzisoxazoles using density functional theory calculations. The results reveal a stepwise (3+2) addition to the C=N double bond, followed by base-assisted N-O bond cleavage and isoxazole ring-opening, leading to oxazoline (via O-cyclization) or imidazolone (via N-cyclization) derivatives. When unsubstituted 1,2-benzisoxazole is used as the substrate, O-cyclization dominates as a kinetically controlled process due to lower activation barriers, while N-cyclization, as a thermodynamically controlled process, is minor. The presence of a methyl group at the C(3) position in 1,2-benzisoxazoles completely blocks N-O bond cleavage, forcing exclusive (3+2) cycloaddition to yield less stable tricyclic products via N-cyclization rather than O-cyclization. These findings align with experimental observations and provide new mechanistic insights into the site selectivity of azaoxyallyl cation cycloadditions. Full article

Readily degradable low-dose hydrate inhibitors are of great significance for flow assurance in the petroleum industry. Recently, α-lipoic acid (LA) was shown to undergo ring-opening reaction via reversible addition–fragmentation chain-transfer copolymerization with acrylamides to introduce labile disulfide bonds into the stable vinyl polymer backbone. Here, LA was copolymerized with acryloyl morpholine (AM) to evaluate their performance as kinetic hydrate inhibitors. Degradability was confirmed for the copolymers with 20 mol.% LA (AM/LA20, M_n = 19 → 9 kDa) after disulfide reduction. Thermogravimetric analysis also indicated faster thermal degradation of AM/LA due to the incorporation of weaker S-S and S-C linkages. Increasing LA content reduced hydrophilicity, and the copolymers were treated with NaOH to ensure water solubility. However, at 700 ppm, poly(AM) homopolymer reduced methane consumption during hydrate growth to 54% with respect to the uninhibited system, while gas consumption for the carboxylate AM/LA20 reached 78%. An advantageous feature of LA is its carboxylic acid, allowing desired functionalities to be grafted onto the degradable copolymer. Isopropyl amine (IPAm) was coupled with LA to form an amide known to be effective during hydrate inhibition (LA(IPAm)). The copolymer AM/LA(IPAm)20 demonstrated better water solubility compared to the original AM/LA20. Furthermore, the desirable IPAm functionality allowed the hydrate inhibition to be re-established at 54%, nearly recovering the performance of the poly(AM) homopolymer. This article assesses the application of LA and LA derivatives as building blocks for degradable amide-based kinetic hydrate inhibitors by validating their degradability with material characterizations and their inhibition performance during structure I hydrate growth. Full article

The growing demand for sustainable and high-performance lubricants has accelerated interest in biolubricants derived from renewable feedstocks. Vegetable oils are attractive candidates due to their biodegradability, low toxicity, and favorable viscosity index. However, their application is limited by poor oxidative and thermal stability. The epoxidation of unsaturated fatty acids offers a versatile route to address these drawbacks by enhancing stability and introducing reactive epoxy groups for further functionalization. This review highlights the advances in the use of epoxidized vegetable oils (EVOs), as platforms for lubricant design. Post-epoxidation modifications, such as ring-opening reactions, crosslinking, hybridization with additives, and click-type chemistries, are critically examined with emphasis on their impact on viscosity, polarity, tribofilm formation, and overall tribological behaviour. Structure–property relationships were discussed to establish design principles linking chemical modifications with lubrication regimes, wear resistance, and film-forming ability. In addition, sustainability aspects, including biodegradability, ecotoxicity, and life cycle assessment, are reviewed to evaluate the trade-offs between performance enhancement and environmental compatibility of these modifications. Current challenges and future perspectives are outlined, including the need for standardized testing protocols, the integration of multifunctional modifications, and predictive modelling tools. By bridging molecular engineering, tribological performance, and sustainability, this review provides a roadmap for the rational design of advanced epoxidized oil-based biolubricants. Full article

Synthesis of 6-(5-mercapto-4R-4H-1,2,4-triazol-3-yl)pyrimidine-2,4(1H,3H)-dione derivatives offer a versatile platform for the development of new heterocyclic compounds. These molecules combine the biologically relevant 1,2,4-triazole ring, known for its antimicrobial and antioxidant properties, with a pyrimidine-2,4-dione core structurally related to vitamin B₁₃ (orotic acid), essential in nucleic acid metabolism. This dual structure opens a wide spectrum of synthetic possibilities, particularly in heterocyclization reactions. The synthesis usually begins with the formation of the triazole ring through cyclocondensation of thiosemicarbazides with appropriate carbonyl precursors, followed by functionalization of the thiol group via S-alkylation or S-arylation. Full article

This work reports progress in the semi-synthetic modification of cassane-type diterpenes isolated from Coulteria platyloba, a plant of ethnopharmacological relevance. The approach involves a sequence of transformations, including oxidative aromatization, ring opening, and Knoevenagel condensation, to generate key intermediates for further diversification. Preliminary studies demonstrated the feasibility of organocatalytic reactions under trienamine activation, including a successful Diels–Alder cycloaddition. The initial steps were achieved with good yields and high purity, underscoring the potential of this strategy to access novel molecular scaffolds through efficient and sustainable methods aligned with the principles of Diversity-Oriented Synthesis (DOS). Full article

In vitro cytotoxicity of three (E)-3-(4′-X-benzylidene)-1-indanones (2a-c) displayed lower cytotoxicity towards murine P388 and L1210 leukemic cells as well as human Molt 4/C8 and CEM T-lymphocytes than the respective six- (3a-c) and seven-membered (4a-c) analogs. To study whether thiol reactivity—as a possible basis of their mechanism of action—correlates with the observed cytotoxicities, kinetics of the non-enzyme catalyzed reactions with reduced glutathione (GSH) and N-acetylcysteine (NAC) of 2a-c were investigated. Furthermore, it was also the aim of the work to compare the thiol reactivity of the open-chain chalcones (1) and their carbocyclic analogs (2-4) with different ring sizes (n = 5–7). The reactivity of the compounds and the stereochemical outcome of the reactions were evaluated using high-pressure liquid chromatography–mass spectrometry (HPLC-MS). Molecular modeling calculations were performed to rationalize the high initial rate and low conversion of the 2a indanone in comparison with those of the carbocyclic analog tetralone (3a) and benzosuberone (4a). Thiol reactivity and cancer cell cytotoxicity showed a dependence on both the ring size and the nature of aromatic substituents. Full article

A versatile, sustainable feedstock pathway to bio-based polymeric materials was developed utilizing lignin biomass and the ring-opening copolymerization (ROCOP) of cyclic anhydrides and epoxides to synthesize functional, lignin-derived, fully bio-based polyester polyols. The initial goal was to make the ROCOP reaction more applicable to bio-derived starting materials and more attractive to commercialization by conducting the polymerization under less constrained and industrially relevant conditions in air and without the extensive purification of reagents, catalysts, or solvents, typically used in the literature. A refined ROCOP system was applied as a powerful tool in lignin valorization by successfully synthesizing the lignin-derived copolyester prepolymers from lignin models and depolymerized native lignin sourced from the reductive catalytic fractionation of Pinus radiata wood biomass. After mechanistic studies based on NMR characterization, an alternative ROCOP-style mechanism was proposed. This was found to be (1) contributing to the acceleration of the observed reaction rates with added [PPNCl] organo-catalyst and (2) ‘self-initiation/self-promoted’ ROCOP without any added external [PPNCl] catalyst, likely due to the presence of inherent [OH] groups/ species in the lignin-derived glycidyl ether monomer promoting reactivity. As a final goal, the potential of these lignin-derived polyesters as intermediate polyols was demonstrated by applying them in the synthesis of polyurethane (PU) film materials with a high biomass content of 75–79%. A dramatic range of thermomechanical properties was observed for the resulting materials, demonstrating how the ROCOP reaction can be used to tailor the properties of the functional polyester and PU material based on the nature of the epoxide and anhydride substrates used. These findings help endeavors towards predicting the relationship between chemical structure and material thermomechanical properties and performance, relevant for industrial applications. Overall, this study demonstrated the proof of concept that PU materials can be prepared from lignocellulosic biomass utilizing industrially feasible ROCOP of bio-derived cyclic anhydrides and epoxides. Full article