Search Results (91)

Pancreatic ductal adenocarcinoma is highly malignant with poor prognosis. Its dense tumor microenvironment severely limits the efficacy of conventional chemotherapy and causes severe side-effects. Herein, we adopt the established Schiff-base crosslinked thermoresponsive injectable self-healing poly(2-(2-methoxyethoxy)ethyl methacrylate-co-oligo(ethylene glycol) methyl ether methacrylate-co-aldehyde 2-hydroxyethyl methacrylate)/carboxymethyl chitosan (APMOH/CMCS) hydrogel as the delivery scaffold. By regulating monomer composition, the volume phase transition temperature (T_VPT) of the hydrogel was tuned to around 43 °C to match the therapeutic temperature requirement. Subsequently, copper–metal organic framework (Cu-MOF) nanoparticles co-loaded with 2,2′-azobis(2-methylimidazoline) dihydrochloride (AIPH) and 2,2′-azinobis(3-ethylbenzothiazoline-6-sulfonic acid) cationic radicals (ABTS·⁺) (denoted as AB@Cu-MOF) were uniformly incorporated into the hydrogel network. Under near-infrared (NIR) irradiation, ABTS·⁺ acts as a photothermal agent to generate hyperthermia for tumor ablation; the elevated temperature further activates AIPH to produce alkyl radicals, which can oxidize inactivated ABTS back to ABTS·⁺ and construct a sustainable photothermal therapy–thermodynamic therapy (PTT-TDT) circulation. Meanwhile, Cu-MOF can consume intracellular glutathione (GSH) to protect active components from deactivation and initiate chemodynamic therapy (CDT) via Fenton-like reactions to produce toxic reactive oxygen species. Benefiting from the thermoresponsive characteristic, the hydrogel undergoes volume shrinkage upon heating, achieving NIR-triggered on-demand drug release with a cumulative release rate of 81.1%. In vitro and in vivo experiments verified that this integrated platform realizes remarkable triple synergistic efficacy of PTT, TDT, and CDT. The tumor volume of the treatment group was merely 13.3% of the control group, and the system also exhibited excellent biocompatibility. Collectively, it offers a feasible and promising intelligent platform for precise local treatment of pancreatic cancer. Full article

This work aims to investigate the interfacial tension characteristics of alkyl carboxymethyl betaines dispersed at the crude oil/formation water interface. Four alkyl dimethyl carboxymethyl betaines and one alkyl diethyl carboxymethyl betaine were synthesized, then the effects of surfactant molecular structure, crude oil component, and inorganic salt composition of formation water on interfacial tensions were studied systematically. The results show that the synthesized octadecyl diethyl carboxymethyl betaine has the highest interfacial activity and exhibits superior anti-dilution performance. In the presence of polyacrylamide, this betaine also displays good anti-adsorption capability. With respect to crude oil components, the resin component, especially the petroleum acid and alkali components, play important roles in tension reduction. For formation water, its alkaline inorganic salts are crucial to obtain an ultra-low interfacial tension by its saponification effect on petroleum acid. The octadecyl diethyl carboxymethyl betaine also exhibits good temperature and salt resistance, but poor tolerance toward divalent cations owing to the consumption of alkaline inorganic salts. Moreover, it is found that there exists synergism between octadecyl diethyl carboxymethyl betaine and dodecylbenzene sulfonate which can further reduce the interfacial tension. The above findings are conducive to the selection of betaine surfactants in chemical flooding. Full article

Ultrashort-chain (USC) per- and polyfluoroalkyl substances (PFAS) are highly polar, mobile, and persistent emerging pollutants. While the environmental distribution of USC species is well-documented, their presence in widely consumed beverages remains under-characterized due to the analytical difficulty of capturing such highly polar species. This study established a robust workflow for the simultaneous determination of C1 to C14 perfluoroalkyl carboxylic and sulfonic acids, alongside other PFAS classes, in diverse beverage matrices including teas and fruit juices. Chromatographic separation was achieved using a mixed-mode inert-coated alkyl-phase LC column to enhance USC retention while maintaining performance for longer-chain analytes. A high-throughput, minimal-handling sample preparation was optimized to mitigate matrix effects and contamination. Method performance was evaluated using fortified beverage samples across 2–500 ng/L, with calibration ranges of 1–2000 ng/L and incorporation of 13 isotopically labeled internal standards. Results demonstrated acceptable accuracy (recoveries within 30% of nominal values) and optimal precision (%RSD < 12%). Application to commercial samples revealed frequent PFAS occurrence, specifically highlighting the prevalence of previously overlooked USC species in the human diet. These results demonstrate that ready-to-drink beverages are a significant pathway for human exposure, necessitating the inclusion of USC compounds in future food safety monitoring and risk assessments. Full article

Proton exchange membranes (PEMs) are essential for fuel cells, yet conventional materials like Nafion suffer from humidity dependence and limited thermal stability. This study introduces sulfonated phenylene-bridged periodic mesoporous organosilicas (PMOs) as promising inorganic–organic hybrid PEMs, synthesized via surfactant-templating with varying alkyl chain lengths for different mesopore sizes. Post-synthetic functionalization involves nitration of phenylene moieties, reduction to amines, and ring-opening of propane or butane sultones to graft sulfonic acid groups via flexible spacers, achieving homogeneous distribution along pore walls. Post-functionalization is confirmed by powder X-ray diffraction (PXRD), revealing preserved 2D hexagonal p6mm ordering and phenylene stacking. N₂ physisorption shows type IV isotherms with reduced pore volumes and pore sizes. ¹H NMR is used to quantify functionalization degrees. Impedance spectroscopy on pressed pellets demonstrates proton conductivities up to 2 × 10⁻³ S cm⁻¹ at 30 °C and 90% RH, depending on the functionalization degree, confirming sulfonic acid-mediated conduction. Full article

Bacillus atrophaeus has considerable potential for development as a microbial pesticide. Optimization of fermentation conditions and the wettable powder (WP) formulation is critical for its industrialization and application in sustainable agriculture. In this study, the fermentation of B. atrophaeus YL84 was optimized using single-factor experiments and response surface methodology. Based on these results, a WP formulation was developed and further optimized. The optimal carbon, nitrogen, and inorganic salt sources were sucrose (13.9 g·L⁻¹), tryptone (11.8 g·L⁻¹), and MgSO₄ (5.9 g·L⁻¹), respectively; optimal fermentation conditions were pH 7.0, 32 °C, and 210 r·min⁻¹. After optimization, the inhibition rate and OD₆₀₀ reached 83.71% and 1.758, respectively. The optimized formulation comprised attapulgite-based powder (79%, as carrier), sodium alkyl naphthalene sulfonate (5.4%) as a wetting agent, PEG-6000 (12.6%), CaCO₃ (2%), and vitamin C (1%). The resulting WP exhibited a spore viability of 2.63 × 10⁹ CFU·g⁻¹, and its 50-fold dilution demonstrated antagonistic activity in vitro against Cytospora pyri (Korla pear valsa canker agent) and biocontrol efficacy in vivo on detached-branch assays. These findings demonstrate that the YL84 WP is a promising candidate for the biological control of Korla pear valsa canker. Full article

To elucidate the microscopic adsorption mechanism of dodecylbenzenesulfonate (DBS⁻) on the surface of anatase TiO₂, this study was conducted based on density functional theory, using the DMol³ module for calculations. Four representative initial configurations including orientation differences in sulfonate, the benzene ring, and the alkyl chain were constructed. The contribution of each functional fragment to adsorption stability and interfacial electron transfer behavior were investigated through geometric optimization, energy calculation, Mulliken population, molecular electrostatic potential analysis, Fukui function, and density-of-states analysis. The results showed that configuration a-101 exhibited a lying orientation and multi-stage synergetic adsorption, with the largest adsorption energy (−210.29 kJ/mol), and it was the most stable configuration. The sulfonate group had the most negative electrostatic potential, and the highest occupied orbital was mainly located on its oxygen atom (O). Additionally, the f⁻ value of the Fukui function of O was the highest, serving as the key electrophilic reaction active site, and formed a Ti-O coordination bond with surface Ti⁴⁺. The benzene ring acted as an electron acceptor and participated in adsorption through π-d weak coupling. Adsorption induced the transfer of an about 0.7 e charge from DBS⁻ to TiO₂. The 2p orbitals of O and the 3d orbitals of Ti overlapped in the range of −5.0~0.45 eV, forming a coordination bond. Full article

Produced water (PW) generated from oil and gas operations poses a significant environmental challenge due to its high salinity and complex organic–inorganic composition. This study evaluates forward osmosis (FO) as an energy-efficient approach for PW treatment by comparing a commercial cellulose triacetate (CTA) membrane and a fabricated electrospun nanofibrous membrane, both modified with a zwitterionic sulfobetaine methacrylate/polydopamine (SBMA/PDA) coating. Fourier Transform Infrared Spectroscopy (FTIR) spectra verified the successful incorporation of SBMA and PDA through the appearance of characteristic sulfonate, quaternary ammonium, and catechol/amine-related vibrations. Scanning electron microscopy (SEM) imaging revealed the intrinsic dense surface of the CTA membrane and the highly porous nanofibrous architecture of the electrospun membrane, with both materials showing uniform coating coverage after modification. Complementary analyses supported these observations: X-ray Photoelectron Spectroscopy (XPS) confirmed the presence of nitrogen, sulfur, and chlorine containing functionalities associated with the zwitterionic layer; Thermogravimetric Analysis (TGA) demonstrated that surface modification did not compromise the thermal stability of either membrane; and contact-angle measurements showed substantial increases in surface hydrophilicity following modification. Gas chromatography–mass spectrometry (GC–MS) analysis of the Permian Basin PW revealed a chemically complex mixture dominated by light hydrocarbons, alkylated aromatics, and heavy semi-volatile organic compounds. FO experiments using hypersaline PW demonstrated that the fabricated membrane consistently outperformed the commercial membrane under both MgCl₂ and Na₃PO₄ draw conditions, achieving up to ~40% higher initial water flux and total solids rejection as high as ~62% when operated with 2.5 M Na₃PO₄. The improved performance is attributed to the nanofibrous architecture and zwitterionic surface chemistry, which together reduced fouling and reverse solute transport. These findings highlight the potential of engineered zwitterionic nanofibrous membranes as robust alternatives to commercial FO membranes for sustainable produced water treatment. Full article

The western hemlock looper, Lambdina fiscellaria lugubrosa (Hulst) is a destructive defoliator of coniferous forests and a major cause of economic losses in forestry. A novel and efficient stereoselective synthesis of the sex pheromone of the western hemlock looper (1, 2 and 3) has been successfully achieved. The synthetic strategy integrates several key transformations, including Evans’ chiral auxiliaries, Grignard cross-coupling, hydroboration–oxidation, sulfone alkylation, and hydrogenation, providing an efficient and scalable approach for sex pheromone production. The three synthesized pheromone components were subsequently tested for their ability to attract Semiothisa cinerearia (Bremer & Grey) using both Y-tube and cage bioassays. Notably, compound 1 exhibited a cross-species attractive effect on S. cinerearia, a species that had not previously been documented to respond to the pheromone of L. fiscellaria lugubrosa. This discovery underscores the potential for cross-species attraction, broadens our understanding of pheromone specificity, and emphasizes the value of stereoselectively synthesized pheromones as molecular tools for cross-species pest monitoring and integrated pest management. Full article

In this study, we investigated environmentally responsive photoluminescence color changes in water using an amphiphilic flavin derivative (1a) functionalized with an alkylsulfonate group. At low concentrations and room temperature, 1a exhibited a green emission. Upon increasing the concentration, thermodynamically stable micelle-like aggregates were formed, leading to a yellow emission. In contrast, under rapid freezing conditions, fibrous aggregates were formed under kinetic control, which also exhibited a yellow emission. These distinct aggregation modes are attributed to the cooperative effects of molecular design: the π-stacking ability of the tricyclic isoalloxazine core, flexible long alkyl chains, and the hydrophilic sulfonate moiety. This work demonstrates photoluminescent color switching based on aggregation-state control of a biogenic and potentially sustainable flavin luminophore, offering a new perspective for designing responsive and sustainable photofunctional materials. Full article

Lignin holds significant promise as a feedstock for biocrude production via hydrothermal liquefaction (HTL). Although lignin HTL has been widely studied, the specific depolymerization pathways associated with distinct lignin structures remain largely unexplored. This study investigates the HTL of four structurally diverse lignins: alkaline (AL), dealkaline (DAL), organosolv (OL), and lignosulfonate (LS) across 270–310 °C to elucidate structure-specific mechanisms governing biocrude yield and composition. AL and OL achieved the highest yields (16.8 ± 0.3% and 16.8 ± 2.5%), with AL-derived biocrude showing the highest carbon content (70.2 ± 0.0%) and HHV (31.0 ± 0.2 MJ/kg). In contrast, DAL and LS produced lower yields and inferior fuel quality due to higher sulfur content and lower carbon enrichment. The structures of AL and DAL, containing fewer methoxy groups, produced guaiacol-rich biocrudes (46.6% and 69.5%). Methylation in AL formed alkyl guaiacols and veratroles, while DAL favored side-chain oxidation. OL retained complex structures, forming syringols and desaspidinol, which contributed to heavier biocrude compounds. Sulfonate groups in LS were stabilized mostly as sulfides, leading to elevated sulfur content. These findings provide mechanistic insight into how lignin structure governs HTL behavior, enabling targeted control of biocrude yield and quality for renewable fuel production. Full article

Bio-based surfactants have demonstrated significant potential as economically viable and environmentally sustainable alternatives to petroleum-derived surfactants, with the global biosurfactant market expanding from USD 4.41 billion in 2023 to a projected USD 6.71 billion by 2032, representing a compound annual growth rate of 5.4%. While conventional surfactants such as alkyl aryl sulfates and alkyl benzene sulfonates exhibit extremely high aquatic toxicity and impose substantial ecological costs, biosurfactants including lipopeptides (surfactin, iturin, fengycin, lichenysin) produced by Bacillus species and glycolipids (rhamnolipids, sophorolipids, trehalose lipids, mannosylerythritol lipids) from Pseudomonas demonstrate superior biodegradability. However, current biosurfactant production costs, ranging from 5 to20 USD/kg, cannot compete effectively with synthetic surfactants, averaging approximately 2 USD/kg, necessitating comprehensive process improvements to achieve commercial viability. The utilization of renewable agricultural feedstocks containing 65–70% carbohydrates, including corn stover, sugarcane bagasse, rice bran, and palm oil mill effluent, has achieved production costs as low as 3.8 USD/kg through advanced optimized pretreatment technologies, enzyme catalysis, simultaneous saccharification and fermentation (SSF), and downstream processes, resulting in cost reductions compared to conventional methods. The implementation of artificial intelligence and machine learning algorithms for bioprocess optimization enables simultaneous optimization of genetic engineering, metabolic pathways, and fermentation parameters, achieving yield improvements and cost reductions, with projections indicating production costs below 2.50 USD/kg being needed in the next decade to achieve cost parity with synthetic surfactants, maintaining economic viability. Full article

An efficient Ni-catalyzed, Mn-mediated denitrogenative cross-electrophile coupling of N-alkyl-1,2,3-benzotriazinones with alkyl tosylates and mesylates for access to o-alkyl secondary benzamides is reported. The method uses inexpensive non-anhydrous dimethyl acetamide (DMA) in combination with tetrabutyl ammonium iodide (TBAI) as a co-catalyst to convert sulfonates into iodides in situ. Scope and limitations of the protocol have been demonstrated by >30 examples with yields up to 91%, showing a large electronic effect from the N-substituent in benzotriazinones. An unexpected steric acceleration has been observed from the core of benzotriazinones, not only promising a highly efficient access to 2-alkyl-2,3-disubstituted benzamides but also shedding light on the rate-limiting steps in the catalytic cycle. Full article

Decatungstate (DT) is a highly promising photocatalyst for dioxygen (O₂)-based reactions but has hardly been applied in the photocatalytic degradation technology of dye. Here, we synthesized hydrophilic DT–SO₃H salts by incorporating tetra-alkyl cations with sulfonic acid groups, aiming to enhance both the water solubility and catalytic efficiency of DT under visible light. Comprehensive characterization of DT–SO₃H using ultraviolet–visible spectroscopy (UV–Vis), Fourier Transform Infrared Spectroscopy (FT-IR), X-ray photoelectron spectroscopy (XPS), Photocurrent (PTC), and Electrochemical Impedance Spectroscopy (EIS) confirmed its improved properties. DT–SO₃H demonstrated outstanding photocatalytic performance, achieving 90% degradation of methyl orange within 25 min under continuous visible light irradiation. This study presents a cost-effective and efficient method for degrading methyl orange, representing a significant advancement in the development of high-performance photocatalysts and opening new avenues for the study and application of photocatalytic dye degradation technologies. Full article

In this paper, polymer inclusion membranes (PIMs) were created using poly(vinyl chloride)-based alkyl sulfonic acid derivatives as ion carriers and dioctyl terephthalate as a plasticizer for the selective separation of Pb(II), Cu(II), and Cd(II) ions from aqueous nitrate solutions. The ion carriers were dinonylnaphthalenesulfonic acid (DNNSA) and nonylbenzenesulfonic acid (NBSA). The influence of the carrier and the plasticizer concentration in the membrane on the transport efficiency was investigated. For the PIM system, 15% wt. of carrier (DNNSA, NBSA), 20% wt. of plasticizer, and 65% wt. of polymer poly(vinyl chloride) PVC were the optimal proportions, with which the process was the most effective. Research on the transport kinetics has shown that the transport of Pb(II) ions through PIMs containing acidic carriers adheres to a first-order kinetics equation, which is characteristic of a facilitated transport mechanism. The activation parameter for these processes suggests that the high performance of these ion carriers is associated with the immobilization of the carrier within the membrane. It was found that PIMs based on DNNSA facilitate the selective separation of Pb(II)/Cu(II) and Pb(II)/Cd(II) mixtures, achieving high separation factors. Full article

Organosulfur compounds are appealing owing to the diverse oxidation states accessible by sulfur, allowing the precise adjustment of their properties. In this study, we report a practical oxidation method that converts sulfides to sulfones by generating chlorine dioxide in situ from sodium chlorite (NaClO₂) and hydrochloric acid (HCl) in organic solvents. Diphenyl sulfide was effectively oxidized to diphenyl sulfone in yields of up to 96% under optimized conditions, with high selectivity in ethyl acetate and acetonitrile solvents. The method is compatible with a wide range of substrates, including various aryl, benzyl, and alkyl sulfides, although reactivity diminishes with sterically hindered or electron-rich substrates. This scalable and environmentally friendly process overcomes challenges associated with aqueous oxidants, such as substrate solubility and side reactions, providing a robust alternative for sulfone synthesis. Full article