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This study aimed to evaluate the combined effects of sulfonation, non-thermal oxygen plasma and silane on the shear bond strength (SBS) of PEEK to resin materials. Two hundred and eighty specimens were randomly divided into four groups: (A) untreated; (B) sulfonation for 60 s; (C) oxygen plasma for 20 min; (D) sulfonation for 60 s and oxygen plasma for 20 min. According to the instructions, 120 samples (N = 30) were coated with silane, adhesive, and resin composites. Each group of bonding specimens was divided into two subgroups (n = 15) to measure immediate and post-aging SBS. The surface morphology and the interface between the samples and adhesive were analyzed through SEM. Physicochemical characteristics of the surface and mechanical properties were determined through XPS, FTIR, light interferometry, contact angle measurement, and three-point bending tests. Sulfonation produced a porous layer of approximately 20 µm thickness on the surface, and the oxygen plasma increased the O/C ratio and oxygen-containing groups of the sample surface. After coating with silane, the SBS values of sulfonated PEEK and plasma-treated PEEK increased (9.96 and 10.72 MPa, respectively), and dual-modified PEEK exhibited the highest SBS value (20.99 MPa), which was significantly higher than that of blank group (p > 0.01). After 10,000 thermal cycles, the dual-modified PEEK still displayed a favorable SBS (18.68 MPa). Sulfonation strengthened the mechanical interlocking between PEEK and the resin while oxygen plasma established a chemical bonding between silane and PEEK. This dual modification of the surface microstructure and chemical state synergistically improved the bond strength of PEEK to resin and resulted in considerable long-term effects. [Display omitted] • A permeable porous layer with rich -OH groups was constructed on the PEEK surface by sulfonation and oxygen plasma. • The combined modification of sulfonation, plasma and silane significantly improved the bond strength of PEEK to resin and resulted in considerable long-term effects. [ABSTRACT FROM AUTHOR]

A four-step synthesis process of bifunctional, noncovalent organocatalysts based on the chiral (1R,2R)-cyclohexane-1,2-diamine scaffold containing a 1,2-benzenediamine H-bond donor was developed. Nucleophilic aromatic substitution of the 2-fluoronitrobenzene derivative with the commercial (1R,2R)-cyclohexane-1,2-diamine was followed by selective alkylation of the primary amino group, reduction of the aromatic nitro group and final derivatization of the primary aromatic amino group, i.e., acylation, sulfonation, reductive alkylation and arylation, leading to the four subtypes of organocatalysts. All new compounds were fully characterized. The prepared organocatalysts (32 examples) were tested in the Michael addition of acetylacetone to trans-β-nitrostyrene, yielding the addition product with incomplete conversions (up to 93%) and enantioselectivities of up to 41% ee. [ABSTRACT FROM AUTHOR]

Exploration on the proton exchange electrolytes with cost-effective and high-performance is critical to the development of energy conversion and storage field. The sulfonated covalent organic framework（TPBD-SO3H） was introduced into the chitosan (CS) matrix to fabricate a series of CS/TPBD-SO3H composite membranes, followed by analysis of their structures and properties. The results indicate that a cross-linking interaction between TPBD-SO3H and CS offers an enhanced thermal stability and optimized mechanical properties of the composite membranes. The tensile strength reached a maximum value of 80. 2 MPa, exhibiting a 201% of improvement compared to the CS membrane. Simultaneously, the cross-linking interaction also brings a reduction in the swelling rate of the composite membranes, with a decrease of approximately ～40% compared to the CS membrane. More importantly, the porous structure of TPBD-SO3H, along with its abundant sulfonic acid groups, plays a crucial role in the efficient proton transportation. The composite membrane exhibiting a proton conductivity of up to 24. 7 mS/cm under conditions of 80 ℃ and 95% RH, which is twice that of the CS membrane. [ABSTRACT FROM AUTHOR]

In petrochemistry, normal paraffins are used mainly as raw materials for the production of alkylbenzenes, alkanesulfonates, synthetic fatty acids, secondary alcohols, a-olefins (thermocracking), internal olefins (dehydrogenation). Currently, the market for synthetic detergents (SMC) is one of the most dynamically developing in the world. According to the forecasts of the leading companies producing alkyl benzenes, in the next 10 years, the demand for intermediates for the production of synthetic detergents is expected to grow both in domestic markets and in the global market as a whole. At hydrotreatment units, a wide fraction of n-paraffins (C9-C20) is released from hydrotreated diesel fuel. After that, the C9-C20 fraction is sent to the pre-fractionation unit of the olefin production unit, where the C14-C17 fraction is separated from the wide fraction. This fraction is marketable and requires preliminary purification from aromatic hydrocarbons. Typically, the content of aromatic hydrocarbons in the crude fraction -14+ is from 0.5 to 2.0 wt%. The residual content of aromatic hydrocarbons in the purified fraction should not exceed 0.01% wt. To remove aromatic hydrocarbons, the -14+ fraction is fed to the oleum treatment unit. At the oleum purification unit, post-treatment is carried out using oleum with a concentration of 20-24% wt. After sulfonation, it is necessary to neutralize with caustic soda. Obtaining dearomatized liquid paraffins from diesel fuel using oleum purification has many disadvantages, since working with fuming sulfuric acid requires a high degree of protection of the human body and the strictest observance of safety regulations. Due to the difficulties in disposing of spent sulfuric acid, plant shutdowns and downtime are not uncommon. This article presents the results of a comprehensive study of the adsorption of aromatic hydrocarbons from higher alkanes on zeolite CaX. The main parameters of statics, dynamics and kinetics of adsorption are determined. [ABSTRACT FROM AUTHOR]

Black liquor is the by-product of the pulping process where the lignin, hemicellulose, and extractive materials are separated from wood to produce paper pulp. As one of the primary lignin sources, black liquor is considered an important energy source from biomass to produce biofuels and value-added chemicals. However, soda alkaline lignin has limited industrial applications due to its insolubility in water and lack of reactivity. Therefore, chemical modification is essential to enhance its industrial applications. In this study, alkali lignin from bagasse was modified through sulfonation, sulfomethylation, and amination processes using different reaction conditions. The structural analysis of obtained products was investigated by FTIR and 1H-NMR. The molecular weight distribution and thermal stability of the water-soluble products were analyzed using gel permeation chromatography (GPC) and thermogravimetric analysis (TGA), respectively. The elemental analysis was used to measure the elements (CHNSO) of the obtained water-soluble derivatives. The chemical structure analysis of the samples with FTIR and 1HNMR confirmed the modification processes. The results indicate that modification led to increased water solubility and a decrease in the precipitation pH of lignin samples, due to the introduction of sulfonate and amin functunal groups on lignin. In addition, the molecular weight and thermal stability of modified lignins were increased due to the presence of sulfonate and amine groups compared to unmodified lignin. [ABSTRACT FROM AUTHOR]

A corncob-derived magnetic solid acid catalyst was synthesized through the sulfonation method and an impregnation process, respectively. In the sulfonation process, the concentrated H2SO4 was utilized as an activation agent to obtain acidic properties. The solution of ferric sulphate-ferrous sulphate was utilized for impregnation to generate the magnetic behaviour of the material. The prepared magnetic acid solid catalyst had a high saturation magnetisation value of 16.48 emu/g and a total acidity of 1.43 mmol/g. The performance of the catalyst was evaluated in the esterification reaction of waste cooking oil. The best result presented 86.12% FFA conversion under reaction conditions of 5% catalyst loading and a 1:15 oil-tomethanol molar ratio at 60oC for 4 h. The catalyst was separated magnetically from the reaction solution and exhibited a good reusability with 61% remaining active after 5 consecutive cycles of reaction. This study resulted in a promising method to obtain magnetic-sulfonated carbonbased catalyst from corncob residue, and it is economical potentially and environmentally friendly for the esterification of low-quality feedstock for biodiesel production. [ABSTRACT FROM AUTHOR]

Herein, furfural was synthesized via dehydration of xylose with γ-valerolactone (GVL) in the presence of sulfonated carbon catalysts prepared from eucalyptus activated carbon (EAC) and sulfonating agents (H2SO4 and TsOH). Influences of pure and mixed sulfonating agents on physicochemical attributes of the obtained sulfonated carbon catalysts were explored using different characterization techniques (BET, FTIR, NH3-TPD, CHNS, XRD, TGA, SEM and total acid density). The process input variables (temperature, solvent/substrate ratio, time and catalyst loading) influencing the dehydration process were optimized using Taguchi design approach. The best H2SO4 (H)/TsOH (T) molar ratio for the mixed acid sulfonated EAC (EAC-H-T) material to catalyze xylose conversion to furfural was 3:2. The total acid density (0.79 ± 0.08 mmol/g), specific surface area (711.9 m2/g) and sulfur concentration (9.77%) of the EAC-3H-2T catalyst were higher compared to other sulfonated EAC materials. Taguchi optimization approach revealed that highest furfural yield (74.61 ± 0.05 %) was achieved at the optimum conditions of 180 °C dehydration temperature, 1.5 wt% catalyst loading, 3.0 h dehydration time and 3 mL/g GVL/xylose ratio. 1H- and 13C NMR analyses conducted on isolated product obtained under optimum conditions confirmed the formation of furfural. In addition, the EAC-3H-2T catalyst exhibited sustained activity after it was reused for six times.

Glycosyl aryl sulfones have gained significant attention due to their diverse range of biological activities. However, a straightforward synthesis under mild conditions remains a challenging endeavor. This work presents the first transition-metal-free glycosyl sulfonation, employing a readily prepared sodium glycosyl sulfinate in conjunction with diaryliodonium salts. The method is compatible with various sugar substrates including unprotected sugar derivatives. Notably, the transfer of an aryl moiety in unsymmetric diaryl iodonium salts is chemoselectively achieved by utilizing an anisyl or TMP fragment as a dummy ligand. Preliminary mechanistic studies suggest that the reaction may proceed through an intramolecular SNAr process with a four-membered ring transition state. [ABSTRACT FROM AUTHOR]

Sulfonation, primarily facilitated by sulfotransferases, plays a crucial role in the detoxification pathways of endogenous substances and xenobiotics, promoting metabolism and elimination. Traditionally, this bioconversion has been attributed to a family of human cytosolic sulfotransferases (hSULTs) known for their high sequence similarity and dependence on 3′-phosphoadenosine 5′-phosphosulfate (PAPS) as a sulfo donor. However, recent studies have revealed the presence of PAPS-dependent sulfotransferases within gut commensals, indicating that the gut microbiome may harbor a diverse array of sulfotransferase enzymes and contribute to detoxification processes via sulfation. In this study, we investigated the prevalence of sulfotransferases in members of the human gut microbiome. Interestingly, we stumbled upon PAPS-independent sulfotransferases, known as aryl-sulfate sulfotransferases (ASSTs). Our bioinformatics analyses revealed that members of the gut microbial genus Sutterella harbor multiple asst genes, possibly encoding multiple ASST enzymes within its members. Fluctuations in the microbes of the genus Sutterella have been associated with various health conditions. For this reason, we characterized 17 different ASSTs from Sutterella wadsworthensis 3_1_45B. Our findings reveal that SwASSTs share similarities with E. coli ASST but also exhibit significant structural variations and sequence diversity. These differences might drive potential functional diversification and likely reflect an evolutionary divergence from their PAPS-dependent counterparts. [ABSTRACT FROM AUTHOR]

Polypropylene (PP)‐based carbon fibers were prepared by sulfonation process of isotactic PP fibers with concentrated sulfuric acid, followed by stress‐less carbonization under nitrogen atmosphere. The stabilization behaviors of PP fiber under different sulfonation temperatures and time were discussed. The carbonization behavior of the stabilized PP fibers under different carbonization temperatures, as well as the mechanical performance of the obtained carbon fibers were investigated. The results indicated that linear PP molecule were effectively converted into thermally stable structure at higher temperature (≥130°C) in short time (2 h) through sulfonation‐desulfonation reaction, among which ordered graphite structure has been formed prior to the carbonization process. Meanwhile, the carbon fibers were considerably densified by increasing the sulfonation temperature and carbonization temperature, and a bulk density of 1.96 g/cm3 was achieved. Moreover, the temperature and time of the sulfonation process as well as the temperature of the carbonization process were regulated, and carbon fibers with tensile strength of 262.3 MPa was obtained, which was superior to that of 208.1 MPa for the linear low density polyethylene‐based carbon fibers reported previously. Isotactic PP was proved to be a promising candidate to develop carbon fibers with tunable graphite structure and mechanical performance. [ABSTRACT FROM AUTHOR]

This review provides an overview of the latest applications of sulfonated molecules in biomaterials. Sulfonation, a chemical modification process introducing sulfonic acid groups, enhances biomaterial properties. This review explores the effect of sulfonation and recent innovations in biomaterial applications. It covers hydrogels, scaffolds, and nanoparticles, emphasizing sulfonation's unique advantages. The impact on cellular responses, including adhesion, proliferation, and differentiation, is discussed. This review also addresses sulfonated biomaterials' role in regenerative medicine, drug delivery, and tissue engineering challenges. It also provides a small overview of the sources and features of marine-derived sulfonated molecules, emphasizing their potential roles in advancing scientific research. As a novel aspect, an unconventional complex, "traditional Chinese medicine" and its sulfonation method have come to the forefront after a thousand years of history. This article concludes with a reflection on current research and future avenues, highlighting sulfonation's transformative potential in biomedicine. [ABSTRACT FROM AUTHOR]

The use of slickwater fluids for fracking is key for accessing unconventional shale/tight‐sand reservoirs. To mitigate the frictional losses observed during the injection, drag reducers like sulfonated polyacrylamides (SPAMs) are added to the slickwater fluids. The current study presents a unique controlled investigation that examines the impact of sulfonic group substitution, ranging from 5 to 25 wt%, in SPAMs. The molecular weight of the polymers is kept constant at ~7.5–7.8 million Daltons. The investigation is two‐pronged: first part is comprised of drag reduction (%DR) performance of the polymers in fluids of varying salinities on a laboratory flow‐loop. The results obtained indicated the inter‐dependence of fluid salinity and sulfonic substitution on the polymer performance; for example, %DR deterioration of SPAM with 5 wt% substitution was 24.7%; to the contrary, the deterioration was only 15.6% for SPAM with 25 wt% substitution with rise in fluid salinity from 150 ppm to 110 k ppm. The second part of study included in development of a physics‐based model where the polymer relaxation response (Weissenberg number) was improvised to accommodate the impact of governing parameters and then, successfully correlated with the %DR performance using phenomenological equations for the studied range of parameters. [ABSTRACT FROM AUTHOR]

Sulfonated poly(ether ether ketone)-poly(ether ketone) (SPEEK-co-PEK-x) copolymers with controlled degree of sulfonation are synthesized by the polycondensation reaction of varying monomer ratios. Compared with the traditional homopolymer sulfonated poly(ether ether ketone) (H-SPEEK), the SPEEK-co-PEK-x copolymer membrane has a high degree of sulfonation and excellent proton conductivity. Meanwhile, it also has favorable mechanical properties and stability. This is attributed to the introduction of the -PEK- segment. The SPEEK-co-PEK-75 membrane exhibits the highest conductivity (0.285 S cm−1) at 80 °C, 100% RH and when tests at 80 °C with 80% RH, the SPEEK-co-PEK-75 membrane reaches 0.0587 S cm−1. In addition, the tensile strength of the SPEEK-co-PEK-75 membrane reaches 47.66 MPa at room temperature. Moreover, the study investigates the impact of key variables on the single-cell performance of SPEEK-co-PEK-x membranes. The measured peak power densities of the SPEEK-co-PEK-75 membrane are 212 mW cm−2 and 495 mW cm−2 at 70% RH and 100% RH, which are 1.3 times and 1.7 times higher than that of the Nafion 117 membrane, respectively. After the 80 h durability test at 80 °C and 80% RH, the voltage of the SPEEK-co-PEK-75 membrane only drops by 4.8%. The presence of the -PEK- segment results in a more compact and connected distribution of hydrophilic ion clusters in the SPEEK-co-PEK-X membrane. This adjustment greatly enhances the performance of the membrane, making it an excellent candidate for proton exchange membrane in H 2 /air fuel cells. [Display omitted] • SPEEK-co-PEK-x is a range of random copolymers with controllable sulfonation degree. • Single cell performance of the SPEEK-co-PEK-x membranes were explored under different conditions. • The SPEEK-co-PEK-75 membrane has excellent durability at low humidity. • The synthesis cost of SPEEK-co-PEK-x is low, and the synthesis process is simple. [ABSTRACT FROM AUTHOR]

Modifications were successfully carried out on the polyvinylidene fluoride (PVDF) flat sheet membrane, involving the sulfonation and adding polyethylene glycol (PEG), along with variations in the coagulation bath temperature (CBT). The primary objective of these modifications was to examine their impact on the physicochemical characteristics of the membrane and its permeability to a creatinine solution. The findings revealed that the sulfonated PVDF/PEG membrane, printed at a temperature of 30 °C, displayed substantial increases in porosity, hydrophilicity, water uptake and swelling degree. It is important to note that modifications to the PVDF membrane led to a reduction in thermal stability and an increase in creatinine transport efficiency. For the unmodified PVDF membranes, the clearance values for creatinine in phosphate buffer and phosphate buffer saline media were 0.43 (Transport = 28.65%) and 0.42 mg/dL (Transport = 28.05%), respectively. Conversely, the highest creatinine clearance values were achieved by the SPP30 membrane (sulfonated PVDF/PEG-CBT 30 °C), measuring 0.64 mg/dL (Transport = 42.81%) for creatinine and 0.60 mg/dL for urea (Transport = 39.66%). These results indicate that the sulfonated PVDF/PEG membrane exhibits strong potential for use in hemodialysis applications. [ABSTRACT FROM AUTHOR]

In this work, the authors present as an innovation, the homogeneous sulfonation of Udel® polysulfone (PSU) with acetylsulfate (ACS) under reflux at 45°C in dichloromethane and inert N2 atmosphere (g) for 1.5 h. Different proportions of ACS were used, obtaining sulfonated products with varying degrees of sulfonation (DS). Confirmation of sulfonated polysulfone (PSU-S), denominated as PSU-SA (high degree of sulfonation) and PSU-SB (low degree of sulfonation), was carried out by FTIR and ¹H NMR. Determination of DS was carried out through thermogravimetric analysis (TGA/DSC), varying indexes between 0.883 and 3.022, which correspond to a sulfonated polymer with ion exchange capacity (IEC) from 1.720 to 4.400 meq/g. The evolution of DS related to methods used was monitored and confirmed by ¹H NRM. Sulfonation is undertaken to enhance the suitability of this polymer for future applications in the production of biofuels, targeting its utilization in catalytic processes for esterification and transesterification mechanisms of oils and fats. [ABSTRACT FROM AUTHOR]

The paper presents the results of the analysis of selected physicochemical parameters of engine oils after their use. The oils were obtained both from urban buses belonging to the fleet of a municipal transport company in Lublin, Poland but also from the city of Pardubice in the Czech Republic. Five samples of 10W40 semi-synthetic oil and four samples of 5W30 synthetic oil were tested. Kinematic viscosity at 40°C and 100°C, oxidation, nitration, sulfonation, total acid number (TAN), total base number (TBN), remaining antiwear additives, water content and glycol content, were assessed using infrared spectroscopy (FTIR). The tests were performed on the basis of the ASTM E2412-10 standard. The article also presents the exceedance of the limit values results for the selected parameters. The results of the research can be used in optimizing the engine oil change interval so that the decision to replace the oil is justified both in economic and technical terms, taking into account the need to maintain the service life of the bus. [ABSTRACT FROM AUTHOR]

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Abstract In the last few decades, sulfonated carbon materials have garnered significant attention as Brønsted solid acid catalysts. The sulfonation process and catalytic activity of sulfonated biochar can be influenced by the aromaticity and degree of condensation exhibited by biochar. However, the relationships between the aromaticity, sulfonating ability, and resultant catalytic activity are not fully understood. In this study, biochar samples pyrolyzed at 300–650 °C exhibiting different aromaticity and degrees of condensation were sulfonated and employed as sulfonate-bearing solid catalysts for hydrolytically removing tylosin. They exhibited excellent hydrolytic performance and their kinetic constants were positively correlated with the total acidity and negatively correlated with their aromaticity. This study has uncovered the relationship between the structure, properties, sulfonating ability, and subsequent hydrolytic performance of biochar samples. It was observed that the aromaticity of biochar decreased as the pyrolysis temperature increased. Lower pyrolysis temperatures resulted in a reduced degree of condensation, smaller ring size, and an increased number of ring edge sites available for sulfonation, ultimately leading to enhanced catalytic performance. These findings provide valuable insights into the fundamental chemistry behind sulfonation upgrading of biochar, with the aim of developing functional catalysts for mitigating antibiotics in contaminated water. Graphical Abstract

Calcium Sulfate Hemihydrate (CSH) with uniform morphology and high crystallinity were successfully prepared by a precipitation-hydrolysis method in a concentrated sulfuric acid solution containing fishbone-derived carbon. The CSH was produced by carbonization of fishbone powder at 500 °C for 2 h, followed by sulfonation with concentrated sulfuric acid for 3 h. The solid mixture was washed until the pH of 2, then left at room temperature for 3 days. Physical properties of synthesized CSH were characterized using Fourier transform infrared (FTIR) spectroscopy, X-ray diffraction (XRD), wavelength dispersive X-ray fluorescence (WDXRF), Scanning Electron Microscope (SEM), nitrogen adsorption-desorption isotherm, and melting point test. It is concluded that the CSH were formed due to hydrolysis of fishbone-derived carbon in a moderately concentrated sulfuric acid solution of carbon-derived fishbone and crystallization into a fibrous octa calcium phosphate (OCP) form. In this research, effect of crystal growth time, effect of pH during the crystal growth, and effect of volume of the solution were also investigated. Copyright © 2023 by Authors, Published by BCREC Group. This is an open access article under the CC BY-SA License (https://creativecommons.org/licenses/by-sa/4.0).

In the present study, an acid catalyst (UiO-66-SO3H) with Brønsted and Lewis acid sites was synthesised for the preparation of highly efficient biodiesel from oleic acid and methanol using chlorosulphonic acid sulfonated metal–organic frameworks (UiO-66) prepared with acetic acid as a moderator. The prepared catalysts were characterised using XRD, SEM, FT-IR and BET. The catalytic efficiency of the sulfonated catalysts was significantly improved and successful sulfonation was demonstrated by characterisation techniques. Biodiesel was synthesised by the one-pot method and an 85.0% biodiesel yield was achieved under optimum conditions of the reaction. The esterification reaction was determined to be consistent with a proposed primary reaction and the kinetics of the reaction was investigated. A reusability study of the catalyst (UiO-66-SO3H) was also carried out with good reproducibility. In conclusion, the present study provides some ideas for the synthesis of catalysts with high catalytic activity for the application in the catalytic preparation of biodiesel.

In this study, orange peel waste was successfully sulfonated with SO3-pyridine complex in 1-allyl-3-methylimidazolium chloride ionic liquid in various reaction conditions. 1H NMR was used to verify the occurrence of the reaction and to select the most promising material for the adsorption experiments. The degree of substitution of the sulfonated orange peel waste used for cobalt and copper removal was found to be 0.82. It was prepared with the reaction temperature and time of 70 ℃ and 60 min respectively and with the SO3-pyridine complex to-peel waste ratio of 5:1. The selected material combined with ultrafiltration removed 98% of copper and 91% of cobalt from single metal solutions and 93% of copper and 83% of cobalt from binary metal solution at pH 5 with adsorbent dosage of 12.5 mg/100 mL and initial metal concentration of 8 mg/L. Preliminary experiments were also performed with apple pomace which was sulfonated in the conditions found best for the orange peel waste. The prepared sulfonated apple pomace proved to be almost as effective in cobalt and copper removal as sulfonated orange peel waste, removing 82% of copper and 77% of cobalt from binary metal solution with 12.5 mg/100 mL dosage at pH 5 and an initial metal concentration of 8 mg/L.

Polyetheretherketone (PEEK) is a frequently utilized orthopedic implant material in clinical settings. However, the adverse inflammatory and immunological reactions due to the PEEK surface after implantation often cause poor osseointegration and thereby hinder its clinical utility. To improve osseointegration and enhance the success rate of PEEK implants, the surface can be biofunctionalized to be immunomodulatory. Consequently, in this study, lithium-doped bioglass nanospheres (Li/BGs) was coated on the sulfonated PEEK surface. Furthermore, we assessed the anti-inflammatory potential of the biofunctionalized PEEK implants and their impact on osteogenesis. In our study, it was observed that the in vitro biofunctionalized PEEK surface exhibited enhanced osteogenesis and immunomodulatory osteogenesis properties, while also effectively suppressing the acute inflammatory response initiated by macrophages. Furthermore, our in vivo experiments demonstrated that the biofunctionalized PEEK surface contributed to improved osteogenesis properties and mitigated the formation of fibrous capsules. Therefore, the in vitro and in vivo results demonstrated that PEEK surface modification with Li/BGs not only changed the disadvantage of being bioinert on the surface but also endowed it with osteoimmunomodulatory regulation and bone-promoting properties. Thus, the biofunctionalized PEEK may be a promising candidate for use as an orthopedic implant in clinical settings.

Biodiesel production from non-edible oils utilizing a highly efficient eco-friendly catalyst is a crucial necessity for replacing fossil fuels. In the present work, biochar has been applied for both energy and environmental purposes. The biochar was made by slow pyrolysis from a variety of biomass, primarily cassava peel, irul wood sawdust, and coconut shell. All biochars were used as adsorbents to remove an anionic dye (methyl orange) by conducting batch adsorption studies. The biochar made from cassava peels showed the highest dye adsorption, and it was characterized using elements analysis (CHNS), Fourier transform infrared spectroscopy (FTIR), X-ray photoelectron spectroscopy (XPS), X-ray diffraction (XRD), scanning electron microscopy (SEM), surface area analyzer (BET), total acid density, and sulfonic acid group density to successfully confirm the presence of weak (–OH) and strong (–COOH, –SO3H) acidic groups. Furthermore, for microwave-assisted biodiesel production from Millettia pinnata seed oil, the dye adsorbed biochar made from cassava peel was utilized as a Brønsted acid catalyst. The catalyst having a surface area of 4.89 m2/g, an average pore width of 108.77 nm, a total acid density of 3.2 mmol/g, and a sulfonic acid group density of 1.9 mmol/g exhibits distinctive mesoporous properties that contribute to a biodiesel yield of 91.25%. By utilizing the catalyst for three more cycles and getting a yield of more than 75%, the reusability of the catalyst was investigated. [ABSTRACT FROM AUTHOR]

In the last few decades, sulfonated carbon materials have garnered significant attention as Brønsted solid acid catalysts. The sulfonation process and catalytic activity of sulfonated biochar can be influenced by the aromaticity and degree of condensation exhibited by biochar. However, the relationships between the aromaticity, sulfonating ability, and resultant catalytic activity are not fully understood. In this study, biochar samples pyrolyzed at 300–650 °C exhibiting different aromaticity and degrees of condensation were sulfonated and employed as sulfonate-bearing solid catalysts for hydrolytically removing tylosin. They exhibited excellent hydrolytic performance and their kinetic constants were positively correlated with the total acidity and negatively correlated with their aromaticity. This study has uncovered the relationship between the structure, properties, sulfonating ability, and subsequent hydrolytic performance of biochar samples. It was observed that the aromaticity of biochar decreased as the pyrolysis temperature increased. Lower pyrolysis temperatures resulted in a reduced degree of condensation, smaller ring size, and an increased number of ring edge sites available for sulfonation, ultimately leading to enhanced catalytic performance. These findings provide valuable insights into the fundamental chemistry behind sulfonation upgrading of biochar, with the aim of developing functional catalysts for mitigating antibiotics in contaminated water. Highlights: Effects of aromatic, condensation and topology of condensed ring in biochar on their sulfonation ability were revealed The total acidity of sulfonated biochar was positively correlated with its hydrolytic ability for tolysin mitigation Low aromaticity, low degree of condensation and abundant edge sites led to high acidity and enhanced catalytic ability [ABSTRACT FROM AUTHOR]

While anion exchange membrane (AEM) water electrolysis has many advantages, its commercialization is impeded by the low alkaline stability of most AEM, due to the fragility of quaternary ammonium groups. Ion solvating membranes (ISM) can be an alternative, but so far require high alkaline concentrations. Here, it is shown that sulfonation of polybenzimidazole results in ISM which swell strongly in 1 m KOH. Crosslinking with dibromoxylene controls the swelling, and after activation conductivities of >100 mS cm−1 can be reached in 1 m KOH. Stability in 1 m KOH at 80 °C is excellent: Conductivity remains unchanged and tensile strength and Young's modulus remains high over the test period of a half year. In an electrolyzer operating with 1 m KOH feed solution at 80 °C, a stable performance is achieved for over 500 h test without failure, suggesting that the high alkaline stability observed in ex situ tests is also achieved in the electrolyzer. [ABSTRACT FROM AUTHOR]

Polyethylene is a promising low-cost alternative precursor material for carbon fiber production, but it has yet to show mechanical properties near or surpassing polyacrylonitrile-derived carbon fibers. The high molecular weight and order of ultra-high molecular weight polyethylene (UHMWPE) may offer a pathway to realizing this promise by enabling long-range graphitic structure formation and superior mechanical properties. The tension applied during the precursor stabilization process is crucial to maintaining the shape of the fibers during the conversion process, but no published study has yet probed the relationship between sulfonation tension and carbon fiber microstructure and mechanical properties. In this work, a logarithmic sweep of tensile stress was applied to UHMWPE fibers during the stabilization process followed by carbonization. Increasing tension significantly reduced fiber shrinkage, resulted in straighter fibers with less severe kink bands, and greatly improved the mechanical properties of the fibers. Raman spectroscopy and X-ray diffraction revealed that in all cases the carbon fibers were largely amorphous, but increasing tension resulted in increased size and alignment of the turbostratic crystallites with the fiber axis. Large voids were present in the sample fibers, so the Griffith-Irwin relation was employed to predict the potential ultimate tensile strength of the fibers with voids reduced to sizes comparable to commercially produced fibers. This work demonstrates the importance of tension applied during the stabilization of polyethylene fibers for carbon fiber production and establishes a framework for achieving high mechanical properties from these precursors. [ABSTRACT FROM AUTHOR]

The sustainable and environmentally benign energy demand of the world has been increasing. Among the various options, proton exchange membrane fuel cell is an attractive choice for energy supply due to its high efficiency and application conditions without waste. In this research, triazole-based ionic liquid doped sulfonated polyether ether ketone (SPEEK) composite membranes were presented for proton exchange membrane fuel cell (PEMFC) applications. Composite membranes were prepared by incorporating 1,2,3-triazole-based ionic liquids (TIL 1-2-3) into poly(ether ether ketone) (PEEK) matrices. The mechanical, structural, and thermal properties of both composite membranes and the triazole-based ionic liquids were thoroughly characterized using dynamic mechanical analysis (DMA), Fourier transform infrared spectroscopy (FTIR), and thermogravimetric analysis (TGA). The performance and viability of composites for PEMFC applications that involve elevated temperatures were conducted by proton conductivity test across a broad range of temperatures (30-180 oC). High-temperature proton conductivity was measured as 1.73x10 -2 S/cm for SPEEK/TIL-3(1.0). According to the proton conductivity test results, it was concluded that the composite membranes may exhibit improved performance in PEMFC applications due to increased proton conductivity values. [ABSTRACT FROM AUTHOR]

Partial enzymatic hydrolysis is a green alternative to chemical processes to facilitate the isolation of cellulose nanofibers (CNFs). In this work, we compared the production of CNFs from two sugarcane bagasse substrates (bleached and bleached-sulfonated) using partial enzymatic hydrolysis with the commercial cocktail Cellic CTec3®, followed by ultrasonication. The effect of pretreatments and enzyme dosage on CNF properties and yields were evaluated. Mild enzymatic hydrolysis applied to sulfonated samples using only 0.312 mg enzyme/g substrate for 6 h increased CNF yield up to 2.5-fold and resulted in micrometer length fibers with an average diameter between 5 and 6 nm, as demonstrated by detailed morphological characterization of the substrates. These results were achieved due to the combination of the delignification steps and sulfonation, which enhanced enzymatic hydrolysis and fibrillation efficiency. Furthermore, combining enzymatic hydrolysis and sulfonation increased the CNF thermal stability (56–111 °C for bleached and 87–97 °C for bleached and sulfonated samples). These results demonstrated a pivotal role of enzymes in green CNF production and revealed the optimized hydrolysis/pretreatment conditions for manufacturing CNFs with advanced properties using enzymatic mixtures. [ABSTRACT FROM AUTHOR]

This work describes the electrochemical synthesis of allyl sulfones via sulfonation of allyl trifluoroborates. The process involves a radical addition to the alkene followed by the elimination of the trifluoroborate moiety, giving access to different substituted allyl sulfones. The efficacy of this reaction is attributed to the β-σ(C–B) stabilization of the electrochemically-generated intermediate carbocation, which plays a pivotal role in enforcing regioselectivity during the process. The reaction system is robust and general, allowing for compatibility with aromatic, heteroaromatic, and aliphatic sulfinate and allylic systems. The protocol is considered an inexpensive, safe, and environmentally friendly method for synthesizing this recognizable organic motifs in both synthetic and medicinal chemistry in absence of mediators or even additional supportive electrolite, as only electrons applied through electrical current are required for the reaction to proceed. Moreover, the continuous flow conditions, which fits into green chemistry standards, have demonstrated the feasibility of electrochemically synthesizing allyl sulfones, resulting in highly favorable outcomes and enabling the potential scalability of the electrochemical process. [ABSTRACT FROM AUTHOR]

Human sulfotransferases 1A3 (SULT1A3) has received particular interest, due to their functions of catalyzing the sulfonation of numerous phenolic substrates, including bioactive endogenous molecules and therapeutic agents. However, the regulation of SULT1A3 expression and the underlying mechanism remain unclear. Here, we aimed to investigate the regulation effects of bile acid‐activated farnesoid X receptor (FXR) on SULT1A3 expression, and to shed light on the mechanism thereof. Our results demonstrated that FXR agonists (CDCA and GW4064) significantly inhibit the expression of SULT1A3 at mRNA and protein levels. In addition, overexpression of FXR led to decrease in SULT1A3 expression and knockdown of FXR significantly induced the expression of SULT1A3 in protein and mRNA levels, confirming that FXR expression manifestly showed negative regulatory effect on basal SULT1A3 expression. Furthermore, a combination of luciferase reporter gene and CHIP assays showed that FXR repressed SULT1A3 transcription through direct binding to the region at base pair positions −664 to −654. In conclusion, this study for the first time confirmed FXR was a negative transcriptional regulator of human SULT1A3 enzyme. [ABSTRACT FROM AUTHOR]

Sulfonyl chlorides are a class of cheap and readily available basic chemicals, which have routinely served as electrophilic reagents in their chemical transformations. Herein, we disclose a novel PPh3‐mediated nucleophilic sulfonation method of sulfonyl chlorides with arynes. Different from the classical P(III)‐mediated reductive deoxygenation reaction of sulfonyl chlorides, the valence state of the sulfur atom has not been changed. This protocol exhibits broad functional group tolerance and provides a direct approach to a variety of aryl and alkyl sulfones. [ABSTRACT FROM AUTHOR]

The aim of this study was to develop and optimize a chiral HPLC-MS/MS method for quantitative analysis of (R)-/(S)-salbutamol and (R)-/(S)-salbutamol-4′-O-sulfate in human urine to allow for bioanalytical quantitation of the targeted analytes and investigations of stereoselectivity in the sulfonation pathway of human phase Ⅱ metabolism. For analytical method development, a systematic screening of columns and mobile phases to develop a separation via enantiomerically selective high performance liquid chromatography was performed. Electrospray ionization settings were optimized via multiple-step screening and a full factorial design-of-experiment. Both approaches were performed matrix-assisted and the predicted values were compared. The full factorial design was superior in terms of prediction power and knowledge generation. Performing a longitudinal excretion study in one healthy volunteer allowed for the calculation of excretion rates for all four targeted analytes. For this proof-of-concept, either racemic salbutamol or enantiopure levosalbutamol was administered perorally or via inhalation, respectively. A strong preference for sulfonation of (R)-salbutamol for inhalation and peroral application was found in in vivo experiments. In previous studies phenol sulfotransferase 1A3 was described to be mainly responsible for salbutamol sulfonation in humans. Thus, in vitro and in silico investigations of the stereoselectivity of sulfotransferase 1A3 complemented the study and confirmed these findings. [ABSTRACT FROM AUTHOR]

Calcium Sulfate Hemihydrate (CSH) with uniform morphology and high crystallinity were successfully prepared by a precipitation-hydrolysis method in a concentrated sulfuric acid solution containing fishbone-derived carbon. The CSH was produced by carbonization of fishbone powder at 500 °C for 2 h, followed by sulfonation with concentrated sulfuric acid for 3 h. The solid mixture was washed until the pH of 2, then left at room temperature for 3 days. Physical properties of synthesized CSH were characterized using Fourier transform infrared (FTIR) spectroscopy, X-ray diffraction (XRD), wavelength dispersive X-ray fluorescence (WDXRF), Scanning Electron Microscope (SEM), nitrogen adsorption-desorption isotherm, and melting point test. It is concluded that the CSH were formed due to hydrolysis of fishbone-derived carbon in a moderately concentrated sulfuric acid solution of carbonderived fishbone and crystallization into a fibrous octa calcium phosphate (OCP) form. In this research, effect of crystal growth time, effect of pH during the crystal growth, and effect of volume of the solution were also investigated. [ABSTRACT FROM AUTHOR]

The present work deals with the fabrication of cost-efficient nanocomposite proton exchange membrane (PEM), prepared by incorporation of nanoparticles of Fly Ash (FA) collected from M/s Bina thermal power plant Madhya Pradesh India; within the host PVDF [poly(vinylidene fluoride)] polymer matrix. Subsequently, the nanocomposite membranes are treated with the well-known sulfonating agent chlorosulfonic acid at 60˚C for 1.5 h. The successful incorporation of FA nanoparticles within the host polymer structure along with the sulfonation of the nanocomposite membranes was confirmed by using FTIR, XRD, FESEM-EDX, and AFM studies. The ion exchange capacity (IEC) and proton conductivity (PC) of nanocomposite membranes are observed to be 0.58 meq g−1 and 3.30 × 10−2 S cm−1 respectively. Further, it was interesting to note that the fabricated membranes exhibited enhanced water uptake capacity up to 19.6% with supressed methanol crossover (1.7 × 10−7cm2/s). Among all the fabricated membranes, the membrane SPF-5 (containing 5% w/w FA), exhibited significantly high membrane selectivity 1.94 × 105 Scm−3 s over corresponding Nafion-117 (2.47 × 104 Scm−3 s), which clearly indicates its potency towards an alternative to costly Nafion-117 for DMFCs (direct methanol fuel cells) application. [ABSTRACT FROM AUTHOR]

The development of photothermal catalysts for biodiesel synthesis reaction (transesterification) requires the production of light-absorbing nanoparticles functionalized with catalytic (acid) groups. Using Stöber method, it is possible to produce resorcinol/formaldehyde resin (RF) nanoparticles, which can be carbonized (pyrolysis in an inert atmosphere) and sulfonated. In this work, vegetable tannins are used as a replacement for synthetic resorcinol in the Stöber synthesis of resin (TF) nanoparticles. The nanoparticles are characterized using DLS, FESEM, TEM and N2 adsorption-desorption isotherms. Both resin and carbon nanoparticles are sulfonated by reaction with concentrated sulfuric acid. The attachment of sulfonic groups is verified by FTIR and EDX. The number of sulfonic groups is measured by acid/base titration and TGA. All sulfonated nanoparticles show catalytic activities towards Fischer esterification of ethanoic acid with ethanol, and high (up to 70%) conversion is obtained. The conversion is lower with TF-based nanoparticles, but the turnover numbers are similar in the RF- and TF-based materials. Sulfonated carbon and resin nanoparticles show higher catalytic activity compared to commercial acidic catalysts (e.g., Nafion®). Photothermal heating of carbon nanoparticles is observed. In Part II, sunflower oil transesterification, catalyzed by sulfonated nanoparticles, is observed. Photothermal catalysis of acetic acid esterification and sunflower oil transesterification is demonstrated. [ABSTRACT FROM AUTHOR]

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Abstract Carbon-based solid acids have been successfully employed as acidic catalysts for pollutant mitigation in wastewater. To fully tap the potentials of commercially viable carbons for the preparation of solid acids and enhance their catalytic performances is a challenging problem. In this work, three commercialized carbons including biochar, activated carbon and graphite were preprocessed (ball-milling, Hummer exfoliation, HNO3 soaking, and microwave heating in HNO3, etc.), sulfonated, and evaluated as solid-acid catalysts for tylosin mitigation. Graphite-originated solid acid performed the best through a balling-milling preprocess, while biochar-originated solid acids behaved well under all preprocessing treatments, in which 40 mg L−1 of tylosin was mitigated within 8 min by 1 g L−1 of biochar-originated solid acids. The biochar solid acid through the ball-milling preprocess presented high total acidity and large amounts of –SO3H groups, due to dramatically increased surface area and the rise of activation groups (hydroxyl, alkyl and alkoxy groups, etc.) facilitating electrophilic reaction. In addition, decreased particle size and aromaticity and increased structural defects also contributed. Theoretical calculation of average local ionization energy (ALIE) of condensed aromatic model molecules with substituted activation groups confirmed the promoting effects on sulfonation from strong to weak were 8.40–9.06 eV. These findings have deepened the knowledge in tuning carbon surface chemistry for better sulfonation, thus strengthening catalytic degradation of tylosin. The value of this study is in pulling a clear thread for maneuvering solid-acid catalysts using carbons, which holds a novel promise for rationally functionalizing biochar-based catalysts for the remediation of macrolide antibiotics in polluted water. Graphical Abstract

Highlights Sulfonated polyvinylidene fluoride (S-PVdF) binders with improved hydrophilicity were synthesized via a simple sulfonation process of conventional hydrophobic PVdF binders. The abundant sulfonate groups of S-PVdF binders significantly improved ionic conduction in thick electrodes (~ 6 mg cm−2), enabling improved reversible capacities under various current densities. The S-PVdF binders effectively suppressed cathode dissolution, resulting in enhanced capacity retention at higher temperature operations (45 °C).

This study prepared sulfonated Camellia oleifera shell biochar using Camellia oleifera shell agricultural waste as a carbon source, and evaluated its performance as a catalyst for preparing biodiesel. The biochar obtained from carbonizing Camellia oleifera shells at 500 °C for 2 h serves as the carbon skeleton, and then the biochar is sulfonated with chlorosulfonic acid. The sulfonic acid groups are mainly grafted onto the surface of Camellia oleifera shell biochar through covalent bonding to obtain sulfonic acid type biochar catalysts. The catalysts were characterized by Scanning Electron Microscope (SEM), X-ray diffraction (XRD), Nitrogen adsorption-desorption Brunel-Emmett-Taylor Theory (BET), and Fourier-transform infrared spectroscopy (FT-IR). The acid density of the sulfonated Camellia oleifera fruit shell biochar catalyst is 2.86 mmol/g, and the specific surface area is 2.67 m2/g, indicating high catalytic activity. The optimal reaction conditions are 4 wt% catalyst with a 6:1 alcohol to oil ratio. After esterification at 70 °C for 2 h, the yield of biodiesel was 91.4%. Under the optimal reaction conditions, after four repeated uses of the catalyst, the yield of biodiesel still reached 90%. Therefore, sulfonated Camellia oleifera shell biochar is a low-cost, green, non-homogeneous catalyst with great potential for biodiesel production by esterification reaction in future development.

There has been a recent uptake in the use of polyether-ether-ketone (PEEK), which is an organic thermoplastic polymer, in the manufacturing of various medical devices, implants, and equipment. Finding the best time and procedure for PEEK after sulfonation is the goal of this research. A total of 30 PEEK discs were sulfonated in this study by immersing them in concentrated (H2SO4) sulfuric acid for various durations and subsequently treated using various post-treatment techniques. Five experiments were carried out, aimed studying the effect of immersion time (5 s–2 min). The methods used as post-treatment were hydrothermal treatment, immersion in NaOH, and washing with acetone. The sulfonation time was measured, and the post-treatment techniques, surface characterizations, were conducted using scanning electron microscopy (SEM) (Electron Optics Instruments, LLC., West Orange, NJ, USA), atomic force microscopy (AFM) (AFM, Vía Burton, CA, USA), and hydrophilic properties. The results were confirmed by attenuated total reflectance-Fourier transform infrared spectroscopy (ATR-FTIR). The findings of this study demonstrate that sulfonating PEEK caused a structure with a porous network to form in every sample. As the sulfonation time increased, the porous structure became more noticeable and the concentration increased. As a consequence, the roughness of the surface increased notably, and the modified PEEK surface’s wettability improved noticeably. Hydrothermal treatment was determined to be the most successful way for eliminating the leftover sulfuric acid, and sulfonation for 2 min was determined to be ideal. By understanding the best post-treatment procedures and ideal sulfonation duration, a theoretical foundation for the production of sulfonated PEEK for orthopedic uses may be laid.

Polystyrene is used widely due to their ease and convenience; however, the life cycle of this kind of plastic is really short due to the single use purpose, therefore, there are a lot of waste released into the environment annually. In this research, single use dishes made from polystyrene waste (PS) were denaturized to have capacity of ion exchanging by sulfonating process with concentrated sulfuric acid as an agent. The results showed that the sulfonated polystyrene waste (SPS) has grey black color, cation exchange capacity of 0.763 eq/L, density 1.089 g/L and no swelling; this means the functional group SO3–H+ was attached on the polymer matrix which made the polystyrene waste become ion exchange resin. Scanning electron microscopy (SEM) and X-ray energy dispersive spectrometer (EDS) analysis were also studied to prove the existence of SO3–H+ groups on the polymer chain with the increase in percentage of sulphur element from 0 to 2.24%. With the optimized sulfonating conditions such as 98% H2SO4 acid volume of 10 mL, reaction time of 10 min, temperature of 80 °C and the mass of polystyrene of 5 g, the calcium removal efficiency was 94.5% with the initial calcium concentration of 200 mg/L. The removal efficiency of heavy metal after 30 min was 98.1%, 95.5% and 98.8% for Zn2+, Cd2+ and Cu2+, respectively. After regeneration process, the sulfonated polystyrene showed the capacity of reusing for ion exchange. With the goal of waste recycling as useful material, the obtained product can be used to remove hardness and heavy metal from water, which helps to limit the exploitation of natural resources, reduce the amount of waste discharged into the environment. However, the adsorption and desorption kinetics, surface area coverage, model kinetics should be studied more to provide a more comprehensive understanding and the feasible application in the real world.

The relevance. Lack of experimental data that allow developing a scientifically based method for calculating and designing film-type reactors, which are also used to produce alkylbenzenesulfonic acids. These acids, in their turn, are currently the main components of synthetic detergents. The issue of increasing reactor equipment efficiency can be most effectively solved using mathematical models built on a physical and chemical basis. The aim. Development of a mathematical model of alkylbenzenes sulfonation, taking into account a substance mass transfer from a gas phase to a liquid phase. Software implementation of the developed model, as well as the use of the developed mathematical model for studying the influence of the process parameters on its efficiency. Object. Alkylbenzenes sulfonation with sulfuric anhydride in a multitube film reactor. Methods. Mathematical modeling is used to perform all computational operations, a modern high-level general-purpose programming language with automatic memory management is used. The quantum-chemical methods for determining thermodynamic parameters of chemical reactions were used. Results. The paper considers the principles of constructing a mathematical model of sulfonation. The authors have developed the calculation program in the Python programming language and assessed the accuracy of description of a real process and the influence of the system technological parameters on a product yield and quality, taking into account a substance interfacial transfer. The system of practical recommendations for improving the alkylbenzenes sulfonation resource efficiency was developed. The mathematical model adequately describes the process. The calculated data are compared with the real data from the operating unit for alkylbenzenes sulfonation with sulfuric anhydride.

Due to its superior mechanical properties and chemical stability, Polyetheretherketone (PEEK) has emerged as an alternative to conventional metal implants. However, the bio-inertness of PEEK's surface has limited its applications. Ambient sulfonation has been adopted to enhance bioactivity, but its nanoscale topographic changes are insufficient for implant-bone interlock. To further improve bone-implant interlock, this study employs CO2 laser machining to create sub-millimeter (0.5 mm) grooves on PEEK's surface, aiming to encourage bone ingrowth and strengthen the implant-bone interface. This research investigated the physical and chemical properties and bio-interaction of PEEK surface modified by sulfonation (SPEEK), laser machining (L-PEEK), and combination of both technique (L-SPEEK). X-ray photoelectron spectroscopy (XPS) spectra revealed that sulfonation compensates for the surface chemical shift instigated by laser ablation, aligning the surface chemistry of L-SPEEK with that of SPEEK. Furthermore, L-PEEK surfaces presented pores with sizes ranging from 1 to 600 μm, while SPEEK surfaces exhibited pores between 5 and 700 nm. All tested samples demonstrated non-cytotoxicity, with L-SPEEK exhibiting the highest mineralization and ALP activity as 2 and 2.1 times that of intrinsic PEEK, after 21 days of incubation. Microscopic imaging reveals a notably higher extracellular content on L-SPEEK compared to the other groups. This study underscores the potential of combining sub-millimeter laser machining with sulfonation in enhancing early osteogenic markers, providing a promising pathway for future PEEK-based orthopedic applications.

Sulfonated poly(ether ether ketone) (SPEEK) materials are promising candidates for replacing Nafion™ in applications such as proton exchange membrane (PEM) and direct methanol fuel cells. SPEEK membranes have several advantages such as low cost, thermal and radiation stability and controllable physicochemical and mechanical properties, which depend on the degree of sulfonation (DS). Commercial PEEK was homogenously sulfonated up to a DS of 60–90% and the membranes were prepared using a solvent casting method. Part of the samples were irradiated with a 10 MeV electron beam up to a 500 kGy dose to assess the ionizing radiation-induced effects. Both non-irradiated and irradiated membranes were characterized by Fourier Transformation infrared (FT-IR) spectroscopy, thermogravimetric analysis (TGA), proton nuclear magnetic resonance (1H-NMR) spectroscopy, electrochemical impedance analysis and, for the first time for non-irradiated membranes, by spectrophotometric analysis with Cr(III). The above-mentioned methods for application for DS assessment were compared. The aim of this study is to compare different methods used for the determination of the DS of SPEEK membranes before and after high-dose irradiation. It was observed that irradiated membranes presented a higher value of DS. The appearance of different new signals in 1H-NMR and FT-IR spectra of irradiated membranes indicated that the effects of radiation induced changes in the structure of SPEEK materials. The good correlation of Cr(III) absorption and SPEEK DS up to 80% indicates that the spectrophotometric method is a comparable tool for the characterization of SPEEK membranes. [ABSTRACT FROM AUTHOR]

A Friedel–Crafts reaction of indolizines with 2‐aryl‐3H‐indol‐3‐ones catalyzed by B(C6F5)3 is described. This protocol gives access to indolizine derivatives that are valuable building blocks in synthetic and pharmaceutical chemistry. The reaction proceeds under mild conditions, affording various C2‐quaternary indolin‐3‐ones based on indolizine with high yields and regioselectivities. Moreover, the synthetic transformations of the target products were realized by N‐methylation and trifluoromethane sulfonation. [ABSTRACT FROM AUTHOR]

The effective administration of medication has advanced over decades, but the medical community still faces significant demand. Burst release and inadequate assimilation are major drawbacks that affect wound healing efficiency, leading to therapy failure. The widespread application of polymers in biomedical research is significant. The polyether ether ketone (PEEK) family is known for its biocompatibility, inertness, and semi-crystalline thermoplastic properties. In our present studies, we have chosen a member of this family, polyether ketone (PEK), to explore its role as a drug carrier. The PEK backbone was subjected to sulfonation to increase its hydrophilicity. The response surface methodology (RSM) was used to optimize the sulfonation process based on the time, degree of sulfonation, and temperature. The PEK polymer was sulfonated using sulfuric acid at 150 °C for 6 h; back titration was performed to quantify the degree of sulfonation, with 69% representing the maximum sulfonation. SPEK and nalidixic sodium salt were dissolved in dichloroacetic acid to create a thin membrane. The physiological and morphological properties were assessed for the SPEK membrane. The studies on drug release in distilled water and a simulated body fluid over the course of 24 h revealed a controlled, gradual increase in the release rate, correlating with a mathematical model and demonstrating the zero-order nature of the drug release. Hemolysis on the SPEK membrane revealed lower toxicity. The SPEK membrane's biocompatibility was established using in vitro cytotoxicity tests on the Vero (IC50: 137.85 g/mL) cell lines. These results confirm that the SPEK membranes are suitable for sustained drug release. [ABSTRACT FROM AUTHOR]

Developing a robust and facile process route for fatty acid methyl ester sulfonate (MES) synthesis is of importance for industrial applications. Herein, Taguchi orthogonal array (OA) approach was used for the first time to establish the optimum process condition for the sulfonation of methyl esters (ME) with chlorosulfonic acid (CSA). According to the experimental design, the most significant parameter was sulfonation temperature, followed by CSA/ME molar ratio. Under the optimum sulfonation conditions (that is, 70°C sulfonation temperature, 2.0 h sulfonation time, 1.5:1 mol/mol CSA/ME molar ratio and 2.0 h aging time), the MES yield and the corresponding signal/noise ratio were 92.08 ± 0.28% and 39.28, respectively. The obtained FTIR and 1H NMR data revealed spectra associated with methyl (CH2 asymmetric and CH2 symmetric stretching vibrations), esters (CO, CO, and OCH3), and sulfonate (SO) groups in the MES sample synthesized under optimal conditions, thus confirming the target MES product. Surface tension measurements revealed that the optimal MES sample had a low critical miscelle concentration of 0.082 g/L at a surface tension of 51.2 mN/m, implying the possibility of better performance. [ABSTRACT FROM AUTHOR]