Search Results (66)

Water-based drilling fluids (WBMs) are widely applied in petroleum engineering due to their lower cost and reduced environmental impact compared to oil-based muds. However, their performance is severely limited in shale formations, where hydration and swelling of clay minerals lead to wellbore instability. In this study, two novel imidazoline-type inhibitors were synthesized from fatty acids: A-Lin (derived from linoleic acid) and A-Lau (derived from lauric acid). The synthesis involved amidation followed by cyclization, and the products were characterized using FTIR and TGA. Their performance as shale hydration inhibitors was evaluated in WBM formulations and compared with commercial additives (Amine NF and Glycol). The FTIR spectra confirmed successful imidazoline ring formation, while TGA demonstrated good thermal stability up to 150 °C, with A-Lin exhibiting superior resistance due to its unsaturated structure. Rheological tests showed that the synthesized additives reduced plastic viscosity, thereby improving cuttings transport efficiency. Swelling tests revealed that A-Lin achieved the lowest final swelling (6.3%), outperforming both commercial inhibitors and the saturated A-Lau analogue. Furthermore, A-Lin provided the best lubricity coefficient (0.148), reducing torque and drag during drilling. Overall, A-Lin demonstrated strong potential as an efficient, thermally stable, and environmentally compatible shale inhibitor for advanced WBM formulations. Compared to conventional inhibitors such as KCl, glycol, and amine-based additives, A-Lin uniquely combines superior swelling inhibition, enhanced lubricity, and good thermal stability, highlighting its novelty as an imidazoline derivative derived from renewable fatty acids Full article

The growing demand for sustainable and efficient synthetic methodologies has brought nanocatalysis to the forefront of modern organic chemistry, particularly in the construction of heterocyclic compounds through multicomponent reactions (MCRs). Among various nanocatalysts, calcium oxide nanoparticles (CaO NPs) have gained significant attention because of their strong basicity, thermal stability, low toxicity, and cost-effectiveness. This review provides a comprehensive account of the recent strategies using CaO NPs as heterogeneous catalysts for the green synthesis of nitrogen- and oxygen-containing heterocycles through MCRs. Key reactions such as Biginelli, Hantzsch, and pyran annulations are discussed in detail, with emphasis on atom economy, reaction conditions, product yields, and catalyst reusability. In many instances, CaO NPs have enabled solvent-free or aqueous protocols with high efficiency and reduced reaction times, often under mild conditions. Mechanistic aspects are analyzed to highlight the catalytic role of surface basic sites in facilitating condensation and cyclization steps. The performance of CaO NPs is also compared with other oxide nanocatalysts, showcasing their benefits from green metrics evaluation like E-factor and turnover frequency. Despite significant progress, challenges remain in areas such as asymmetric catalysis, industrial scalability, and catalytic stability under continuous use. To address these gaps, future directions involving doped CaO nanomaterials, hybrid composites, and mechanochemical approaches are proposed. This review aims to provide a focused and critical perspective on CaO NP-catalyzed MCRs, offering insights that may guide further innovations in sustainable heterocyclic synthesis. Full article

In alkaline water electrolysis, conventional polymer binders like Nafion suffer from poor hydroxide conductivity and inadequate interfacial properties. Herein, a thermally cyclized polyacrylonitrile (CPAN) binder system with a conjugated ladder structure is introduced. The CPAN binders are synthesized by controlled thermal treatment under various temperatures, among which CPAN-400 demonstrates the optimal 57.03% pyridinic N content, provides π-conjugated pathways for enhanced electronic conductivity, and indicates hierarchically porous electrode architectures. The NiFe/CPAN-400 electrode achieves enhanced oxygen evolution performance with an overpotential of 354 mV at 100 mA cm⁻², which is 153 mV and 103 mV lower than NiFe–Nafion and NiFe–PAN, respectively. This enhancement results from synergistic effects, including an electrochemically active surface area increased 2.3-fold, improved electrolyte wettability, and optimized charge transfer kinetics. The pyridinic nitrogen-enriched structure also facilitates a rate-determining step transition from charge transfer to *OOH formation, with a Tafel slope of 59.9 mV dec⁻¹. This work establishes thermally induced polymer cyclization as a versatile strategy for advanced binder developments. Full article

Enhancing the safety of lithium-ion batteries (LIBs) by replacing flammable electrolytes is a key challenge. Ionic liquid (IL)-based electrolytes are considered an interesting alternative due to their thermal and chemical stability, high voltage stability window, and tunable properties. This study investigates the electrochemical behavior of two newly synthesized ILs, comparing them to conventional alkyl carbonate-based electrolytes. Nitrogen-doped carbon silicon oxycarbide (NC-SiOC), used as the active material in negative electrodes, was combined with two polymeric binders: poly(acrylic acid) (PAA) and poly(acrylonitrile) (PAN). NC-SiOC/PAN electrodes exhibited a significantly higher initial charge capacity—approximately 25–30% greater than their PAA-based counterparts in the first cycle at 0.1 A g⁻¹ (850–990 mAh g⁻¹ vs. 600–700 mAh g⁻¹), and demonstrated an improved initial Coulombic efficiency (67% vs. 62%). Long-term cycling stability over 1000 cycles at 1.6 A g⁻¹ retained 75–80% of the initial 0.1 A g⁻¹ capacity. This outstanding performance is attributed to the synergistic effects of nitrogen-rich carbonaceous phases within the NC-SiOC material and the cyclized-PAN binder, which facilitate structural stability by accommodating volumetric changes and enhancing solid electrolyte interphase (SEI) stability. Notably, despite the lower ionic transport properties of the IL electrolytes, their incorporation did not compromise performance, supporting their feasibility as safer electrolyte alternatives. These findings offer one of the most promising electrochemical performances reported for SiOC materials to date. Full article

Aromathecin compounds—which contain the same indolizine core structure as camptothecin-like compounds—are expected to show anticancer activity. Among them, 22-hydroxyacuminatine—which has a substituent on the E-ring of the pentacyclic scaffold—exhibits topoisomerase 1 inhibitory activity; therefore, the development of efficient methods for its synthesis has been actively pursued. Herein, we report a versatile synthetic methodology for introducing various substituents on the E-ring, leading to the total synthesis of 22-hydroxyacuminatine as a model compound of the aromathecin family. The synthesis comprises the following key steps: the synthesis of an isoquinoline N-oxide via the thermal cyclization of 2-alkynylbenzaldehyde oxime, the subsequent Reissert–Henze-type reaction to yield an isoquinolone, and the construction of the indolizine moiety (CD-ring) through C–N bond formation via the Mitsunobu reaction. Consequently, a pentacyclic benz[6,7]indolizino[1,2-b]quinolin-11(13H)-one framework is obtained. Using this methodology, the total synthesis of the natural products norketoyobyrine and naucleficine and an intermediate of the latter, which are indoloquinolizidine-type alkaloids, was achieved, and their antiproliferative activity against HCT-116 human colon cancer cells and HepG2 human liver cancer cells was assessed. Naucleficine and its intermediate exhibited moderate antiproliferative activity against HCT-116 cells, with IC₅₀ values of 55.58 and 41.40 μM, respectively. Full article

This review focuses on photocyclization reactions involving alkenes and arenes. Photochemistry opens up synthetic opportunities difficult for thermal methods, using light as a versatile tool to convert stable ground-state molecules into their reactive excited counterparts. This difference can be particularly striking for aromatic molecules, which, according to Baird’s rule, transform from highly stable entities into their antiaromatic “evil twins”. We highlight classical reactions, such as the photocyclization of stilbenes, to show how alkenes and aromatic rings can undergo intramolecular cyclizations to form complex structures. When possible, we explain how antiaromaticity develops in excited states and how this can expand synthetic possibilities. The review also examines how factors such as oxidants, substituents, and reaction conditions influence product selectivity, providing useful insights for improving reaction outcomes and demonstrating how photochemical methods can drive the development of new synthetic strategies. Full article

The results of rheological studies and thermal analysis of polymer compositions based on polyacrylonitrile copolymers (PAN) of different molecular weights and asphalt isolated by n-pentane solvent deasphalting are presented. It was found that the asphalt content in mixtures with PAN at the level of 10–30 wt.% improves the rheological properties of the polymer composite melt. In particular, the temperatures of extrusion and molding of fibers tend to reduce, and the time during which the melt retains its rheological characteristics necessary for extrusion is notably increased, from 43 to 92 min. Thermal analysis by DSC revealed no effect of asphalt additive in an amount of up to 30 wt.% on radical PAN cyclization and the subsequent stage of fiber stabilization. Our study proved the possibility of preparing polymer composites based on PAN and asphalt suitable for extrusion and eventual molding of continuous filaments of synthetic fibers with reduced cost of production. Full article

Highly-effective non-halogenated flame retardants have received widespread attention because they are environmentally friendly, with low toxicity and low smoke density. In this work, interlayer-functionalized graphene (fRGO) containing silicon and phosphorus elements was synthesized via hydrolytic condensation with 3-(methacryloyloxy)propyltrimethoxysilane and addition reaction with 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide. Interlayer spacing and oxygen-containing groups of reduced graphene oxide (RGO) were regulated by controlling the hydrazine hydrate dosage. Then, phosphorus–silicon-containing organic molecules were inserted into RGO interlayers; this was verified by FTIR, XPS, TEM, etc. The fRGO was added to a polyacrylonitrile (PAN) matrix using a solution blending method to prepare polyacrylonitrile (PAN) composites. The fRGO addition caused the significant decrease in cyclization heat and the considerable increase in char residues, indicating improved thermal stability. Importantly, PAN composites exhibited outstanding flame-retardant properties, with the peak heat release rate reduced by 45%, which is ascribed to the dense graphitic carbon layers induced by phosphorus–silicon-containing organics and the 2D barrier effect of RGO layers to prevent the heat and mass transfer. Full article

By treatment of the peracetylated methylester of 4-acetylamino-2,4-dideoxy-d-glycero-d-galacto-octonic acid (ADOA-PAE) with nitrosyl tetrafluoroborate, a serendipitous formation of a highly functionalized carbohydrate–pyrazole conjugate was observed in 95% yield. This observation is remarkable, as it involves a five-step one-pot synthesis that proceeds via an 1,3-acyl shift and a 1,5-electrocyclization, which usually requires thermal conditions; however, the reaction occurred at a temperature of 0 °C. Additionally, the excellent yield of the carbohydrate-decorated pyrazole and the regiospecificity of the cyclization are of particular interest, as regioselectivity is always a challenge in pyrazole synthesis. Subsequently, this novel access to pyrazoles starting from N-acetyl-allyl amides via nitrosation and electrocyclization was investigated. In addition, mechanistic studies for the formation of substituted pyrazoles of type were carried out. Full article

Binary and ternary copolymers of acrylonitrile (AN), tert-butyl acrylate (TBA), and n-butyl acrylate (BA) are synthesized through conventional radical polymerization in DMSO in the presence of 2-mercaptoethanol. The thermal behavior of binary and ternary copolymers is studied under argon atmosphere and in air. It is demonstrated that the copolymers of AN contain 1–10 mol.% of TBA split isobutylene upon heating above 160 °C, resulting in the formation of the units of acrylic acid in the chain. The carboxylic groups formed in situ are responsible for the ionic mechanism of cyclization, which starts at lower temperatures compared with pure polyacrylonitrile (PAN) or AN copolymer with BA. The activation energy of cyclization through ionic and radical mechanisms depends on copolymer composition. For the ionic mechanism, the activation energy lies in the range ca. 100–130 kJ/mole, while for the radical mechanism, it lies in the range ca. 150–190 kJ/mole. The increase in the TBA molar part in the copolymer is followed by faster consumption of nitrile groups and the evolution of a ladder structure in both binary and ternary copolymers. Thus, the incorporation of a certain amount of TBA in PAN or its copolymer with BA allows tuning the temperature range of cyclization. This feature seems attractive for applications in the production of melt-spun PAN by choosing the appropriate copolymer composition and heating mode. Full article

A Sonogashira coupling of meta-iodocalix[4]arene with various terminal acetylenes confirmed that the meta position of calixarene is well addressable, and that both thermal and microwave protocols led to good yields of alkynylcalixarenes. Alkynes thus obtained were subjected to the ferric chloride and diphenyl diselenide-promoted electrophilic closure. It turns out that the calix[4]arenes give completely different bridging products than those described for the non-macrocyclic starting compounds. This can be demonstrated not only by the isolation of products with a six-membered ring (6-exo-dig), but mainly by the smooth formation of the 5-endo-dig cyclization, which has never been observed in the aliphatic series. An attempt at electrocyclization led to a high yield of the 1,2-diketone (oxidation of the starting alkyne), again in contrast to the reaction described for the acyclic derivatives. The structures of the unexpected products were unequivocally established by X-ray analysis and clearly demonstrate how the preorganized macrocyclic skeleton favors a completely different regioselectivity of cyclization reactions compared to common aliphatic compounds. Full article

In this study, we successfully synthesized a novel triacid monomer by means of the thermal cyclization reaction. Subsequently, a series of nitrogen-rich (A₃+B₂)-type fluorinated hyperbranched poly(amide-imide)s (denoted as PAI-1 and -2, respectively) were prepared by means of a one-pot method using this triacid monomer and a diamine monomer with a triphenylamine-carbazole unit as precursors. The degree of support of the prepared hyperbranched PAIs was found to be about 60% via ¹H NMR calculations. Through X-ray photoelectron spectroscopy (XPS), it was found that the binding energies of C-N (398.4 eV) and -NH (399.7 eV) became lower under a current, while the binding energy peak of N⁺ appeared at 402.9 eV. In addition, the PAIs have good solubility and thermal stability (T_gs: 256–261 °C, T_10%: 564–608 °C). Cyclic voltammetry (CV) analysis shows that the hyperbranched PAI films have good redox properties, and a range of values for the HOMO (4.83 to 4.85 eV) versus LUMO (1.85 to 1.97 eV) energy levels are calculated. The PAI films have excellent electrochromic properties: PAI-1 on coloration efficiency (CE) and transmittance change (ΔT, 852 nm) are 257 cm²/C and 62%, respectively, and have long-lasting redox properties (100 cycles). In addition, we conduct iodine adsorption tests using the structural features of PAIs with electron-drawing units, and the results show that PAI-1 had a high adsorption capacity for iodine (633 mg/g). Full article

Highly efficient one-pot synthesis of hexakis(m-phenyleneimine) macrocycle Cm6 from acetalprotected AB-type monomer, m-aminobenzaldehyde diethylacetal, was successfully achieved based on imine dynamic covalent chemistry and precipitation-driven cyclization. The structure of Cm6 in the solid state was determined using CP/MAS NMR, X-ray single crystallographic analysis, and WAXD. Macrocycle Cm6 is composed of six phenylene and imine bonds facing the same direction, with nitrogen atoms arranged on the outside of the ring, and has a chair conformation, as predicted from DFT calculation. The macrocycle forms π-stacked columnar aggregates and hexagonally closest-packed structure. The cyclization process was investigated using MALDI-TOF MS and NMR. A mechanism of precipitation-driven cyclization based on imine dynamic covalent chemistry and π-stacked columnar aggregation is proposed. Both the nature of imine linkage and the shape anisotropy of the macrocycle played an important role in the single one-pot synthesis. The water-mediated mutual conversion between macrocycle Cm6 and linear oligomers driven by thermal stimulation was analyzed using MALDI-TOF MS and GPC methods. Macrocycle Cm6 with a dynamic covalent imine bond exhibited self-healing properties when stimulated using heat. Full article

Interest in covalent organic frameworks as high-value materials has grown steadily since their development in the 2000s. However, the great advantage that allows us to obtain these crystalline materials—the reversibility of the bonds that form the network—supposes a drawback in terms of thermal and chemical stability. Among the different strategies employed for the stabilization of imine-based Covalent Organic Frameworks (COFs), cycloaddition and other related cyclization reactions are especially significant to obtain highly stable networks with extended π-delocalization and new functionalities, expanding even further the potential application of these materials. Therefore, this entry gathered the most recent research strategies for obtaining stable COFs by means of cyclization reactions, including the Povarov reaction and intramolecular oxidative cyclization reactions as well as some other recent innovative approaches. Full article

In order to adjust the properties of polyamide 6 (PA6) and expand its application, a new strategy of introducing an aromatic imide structure into the PA6 chain through the random copolymerization method is reported. The diimide diacid monomer was first synthesized by the dehydration and cyclization of pyromellitic dianhydride and 6-aminocaproic acid before it reacted with 1,6-hexamethylene diamine to form poly(amide imide) (PAI) salt, and finally synthesized PA6/PAI random copolymers containing an aromatic imide structure by the random copolymerization of ε-caprolactam and PAI salt. The introduction of an aromatic imide structural unit into the PA6 chain could have a great influence on its properties. As the content of PAI increases, the crystallinity (X_c) and melting temperature (T_m) of the PA6/PAI random copolymer gradually decrease, but its glass transition temperature (T_g) increases obviously. When the PAI content is 20 wt%, the copolymer PA6/PAI-20 has the best comprehensive performance and not only has high thermal stabilities but also excellent mechanical properties (high strength, high modulus, and good toughness) and dielectric properties (low dielectric constant and dielectric loss). Moreover, these properties are significantly superior to those of PA6. Such high-performance PA6 random copolymers can provide great promise for the wider applications of PA6 materials. Full article