Phenyl Sulfone Research Articles

Dye Separation and Antibacterial Activities of Polyaniline Thin Film-Coated Poly(phenyl sulfone) Membranes.

We fabricated a nanofiltration membrane consisting of a polyaniline (PANI) film on a polyphenylsulfone (PPSU) substrate membrane. The PANI film acted as a potent separation enhancer and antimicrobial coating. The membrane was analyzed via scanning electron microscopy and atomic force microscopy to examine its morphology, topography, contact angle, and zeta potential. We aimed to investigate the impact of the PANI film on the surface properties of the membrane. Membrane performance was then evaluated in terms of water permeation and rejection of methylene blue (MB), an organic dye. Coating the PPSU membrane with a PANI film imparted significant advantages, including finely tuned nanometer-scale membrane pores and tailored surface properties, including increased hydrophilicity and zeta potential. The PANI film also significantly enhanced separation of the MB dye. The PANI-coated membrane rejected over 90% of MB with little compromise in membrane permeability. The PANI film also enhanced the antimicrobial activity of the membrane. The bacteriostasis (BR) values of PANI-coated PPSU membranes after six and sixteen hours of incubation with Escherichia coli were 63.5% and 95.2%, respectively. The BR values of PANI-coated PPSU membranes after six and sixteen hours of incubation with Staphylococcus aureus were 70.6% and 88.0%, respectively.

Synthesis, structure and catalytic study of a new sandwiched-type vanadoselenite

A novel sandwiched-type vanadoselenite with the formula of K6H8[(SeV10O28(SeO3)3)2(Ni(H2O)4)]·24H2O (1) has been synthesized in aqueous medium and well characterized. Single crystal X-ray diffraction indicates that the sandwiched polyanion [(SeV10O28(SeO3)3)2(Ni(H2O)4)]14− consisted of two trivicant Keggin building units [SeV10O28(SeO3)3]8− and one interconnected Ni2+ ion. Experimental results demonstrated that it could serve as a heterogeneous catalyst for sulfoxidation of thioethers and performed effectively catalytic activity. Under the optimized reaction condition, methyl phenyl sulfoxide could be oxidized to methyl phenyl sulfones within 1 h by using 1 mmol of the substrate, 3 mmol of TBHP and 2 μmol of the catalyst 1 at 25 °C in methanol. Moreover, catalyst 1 can also be easily recycled and reused four times without obvious decrease of catalytic activity.

Intramolecular benzyl cation transfer in the gas-phase fragmentation of protonated benzyl phenyl sulfones.

In this study, the gas-phase fragmentations of protonated benzyl phenyl sulfones were investigated by electrospray ionization tandem mass spectrometry (ESI-MSn ). Upon collisional activation, several characteristic fragment ions were observed, and the similar results occurred with different substituted benzyl phenyl sulfones. A mechanism involving an intramolecular benzyl cation transfer and the formation of intermediate ion was proposed and further identified by density functional theory (DFT) calculations. In addition, a reference compound, benzenesulfinic acid benzyl ester, has been synthesized, and its protonated ion has the same gas-phase behavior as compared to the protonated benzyl phenyl sulfone. This work provides access to some insight into the intramolecular benzyl-transfer reactions of benzyl phenyl sulfones in the gas phase and orients the characteristic peaks in collision-induced dissociation spectrometry (CID-MS).

Laboratory evaluation of an efficient low interfacial tension foaming agent for enhanced oil recovery in high temperature flue-gas foam flooding

Flue-gas foam/surfactant polymer flooding is a novel technology to enhanced oil recovery for heavy oil reservoir after hot water flooding with safety and efficiency. However, high temperature and the complex composition of flue gas greatly influence the foaming ability of the foaming agent, and weaken the plugging and profile control ability of the foam. Hence, screening suitable foam agents is of great significance. Here, a typical terpolymer of N‒methyl butenone carboxylates, alkyl phenyl sulfonates and pyrrolidone was selected as an efficient foam agent. The foaming performance and stability of the foam agent remained unchanged after 300 °C aged for 72 h in the flue gas atmosphere. Foam performance and stability tests in the simulative flue gas environment, adsorption properties of oil sands, and resistance factor evaluation were carried out. It showed good foam performance and stability, low adsorption capacity (0.77 mg/g), low interfacial tension (10−2 mN/m) and high resistance factor (>418), which indicated that the terpolymer (PNCAS) can reduce the gas channeling and increase the sweep area. The results of homogeneous and heterogeneous model experiments and microscopic mechanism suggested that foam flooding can greatly improve oil recovery while the low permeable sand-pack recovery can increase almost 42% in comparison with the conventional hot water flooding.

Study of Organic Sulfide Oxidation on the Modified Graphite Electrodes by Co, Fe and Ni Nano Particles

Electro-oxidation of methyl phenyl sulfide with the aim of producing sulfoxide and sulfone was investigated over Ni, Co, Fe, and their alloys on graphite electrodes in the acetic acid as a non-toxic solvent. The modified electrodes were prepared by cyclic voltammetry technique. The surface morphology of electrodes was investigated by scanning electron microscopy and the presence of metal nanoparticles on the graphite was investigated by X-ray diffraction. The catalytic treatment and synergistic effects of the modified electrodes were studied by electrochemical techniques such as cyclic voltammetry (CV) and chronoamperometry (CA). It was found the performance of all the modified electrodes is successful. In the attendance of methyl phenyl sulfide, the graphite/CoFe modified electrode (G/CoFe) showed the highest performance for electro-oxidation also there was a linear relationship between the square root of the scan rate and anodic current in low scan rates, that indicates a diffusion controlled process. The diffusion coefficient, heterogeneous electron transfer rate constant and electron transfer coefficient were determined for methyl phenyl sulfide electrochemical oxidation. Electro-oxidation of methyl phenyl sulfide by electrolysis method was investigated and its results were studied by gas chromatograph (GC). Based on GC studies, the electro-oxidation of methyl phenyl sulfide by electrolysis produced methyl phenyl sulfoxide and methyl phenyl sulfone. Also, a mechanism for electro-oxidation of sulfide was proposed. The using of non-noble metals as the electrocatalyst for the first time for the organic sulfide electro-oxidation, the very easy, affordable and fast preparation of the modified electrode, high performance of the modified electrode, no need of using oxidant and co-catalyst and designing a homogeneous media with proper conductivity for oxidation of insoluble in water compounds demonstrate important items for the use of this procedure and electrode in the subsequent investigation of sulfides.

Determination of Chemical Inhibitor Efficiency against Intracellular Toxoplasma Gondii Growth Using a Luciferase-Based Growth Assay.

Toxoplasma gondii is a protozoan pathogen that widely affects the human population. The current antibiotics used for treating clinical toxoplasmosis are limited. In addition, they exhibit adverse side effects in certain groups of people. Therefore, discovery of novel therapeutics for clinical toxoplasmosis is imperative. The first step of novel antibiotic development is to identify chemical compounds showing high efficacy in inhibition of parasite growth using a high throughput screening strategy. As an obligate intracellular pathogen, Toxoplasma can only replicate within host cells, which prohibits the use of optical absorbance measurements as a quick indicator of growth. Presented here is a detailed protocol for a luciferase-based growth assay. As an example, this method is used to calculate the doubling time of wild-type Toxoplasma parasites and measure the efficacy of morpholinurea-leucyl-homophenyl-vinyl sulfone phenyl (LHVS, a cysteine protease-targeting compound) regarding inhibition of parasite intracellular growth. Also described, is a CRISPR-Cas9-based gene deletion protocol in Toxoplasma using 50 bp homologous regions for homology-dependent recombination (HDR). By quantifying the inhibition efficacies of LHVS in wild-type and TgCPL (Toxoplasma cathepsin L-like protease)-deficient parasites, it is shown that LHVS inhibits wild-type parasite growth more efficiently than Δcpl growth, suggesting that TgCPL is a target that LHVS binds to in Toxoplasma. The high sensitivity and easy operation of this luciferase-based growth assay make it suitable for monitoring Toxoplasma proliferation and evaluating drug efficacy in a high throughput manner.

Asymmetric synthesis of CF2-functionalized aziridines by combined strong Brønsted acid catalysis.

A diastereo- and enantioselective approach to access chiral CF2-functionalized aziridines from difluorodiazoethyl phenyl sulfone (PhSO2CF2CHN2) and in situ-formed aldimines is described. This multicomponent reaction is enabled by a combined strong Brønsted acid catalytic platform consisting of a chiral disulfonimide and 2-carboxyphenylboronic acid. The optical purity of the obtained CF2-substituted aziridines could be further improved by a practical dissolution–filtration procedure.

Removal of Dye from a Leather Tanning Factory by Flat-Sheet Blend Ultrafiltration (UF) Membrane.

In this work, a flat-sheet blend membrane was fabricated by a traditional phase inversion method, using the polymer blends poly phenyl sulfone (PPSU) and polyether sulfone (PES) for the ultrafiltration (UF) application. It was hypothesized that adding PES to the PPSU polymer blend would improve the properties of the PPSU membrane. The effect of the PES concentration on the blend membrane properties was investigated extensively. The characteristics of PPSU-PES blend membranes were investigated using atomic force microscopy (AFM), scanning electron microscopy (SEM), contact angle measure, and contaminant (dye) elimination efficiency. This study showed that PES clearly affected the structural formation of the blended membranes. A considerable increase in the average roughness (about 93%) was observed with the addition of 4% PES, with a higher mean pore size accompanied by a rise in the pores’ density on the surface of the membrane. The addition of up to 4% PES had a significant influence on the hydrophilic character of the PPSU-PES membrane, by lowering the value of the contact angle (CA) (i.e., to 56.9°). The performance of the PPSU-PES composite membranes’ UF performance was systematically investigated, and the membrane pure water permeability (PWP) was enhanced by 25% with the addition of 4% PES. The best separation removal factor achieved in the current investigation for dye (Drupel Black NT) was 96.62% for a PPSU-PES (16:4 wt./wt.%) membrane with a 50% feed dye concentration.

The Enantiomers of Trinorbornane and Derivatives Thereof

AbstractHerein, we report the synthesis of the enantiomers of trinorbornane, a tetracyclic saturated hydrocarbon with the chemical formula C11H16. The preparation of these rigid carbon scaffolds was enabled by the successful chiral separation of its tricyclic precursor, thus allowing the enantiomers to be synthesized through a reductive radical cyclization reaction. Assignment of the absolute conformation of the enantiomers was achieved through VCD experiments. Further, we report an alternative cyclization procedure providing access to hydroxyl and phenyl sulfone functionalized trinorbornanes.

A Set of phenyl sulfonate metal coordination complexes triggered Biginelli reaction for the high efficient synthesis of 3,4‐dihydropyrimidin‐2(1H)‐ones under solvent‐free conditions

Three new metal coordination complexes, namely, [Co (DPE)(H2O)4](DPE)(BS)2 (1), [Co (DPE)2(H2O)4](ABS)2 (2), [Co (DPE)(H2O)4](MBS)2(CH3OH)2 (3) [DPE = (E)‐1,2‐di (pyridin‐4‐yl) ethene, BS = phenyl sulfonic acid, ABS = p‐aminobenzene sulfonic acid, MBS = p‐methylbenzene sulfonic acid] were obtained under hydrothermal conditions. Complexes 1‐3 were structurally characterized by X‐ray single‐crystal diffraction, powder X‐ray diffraction and IR. Complexes 1 and 3 exhibit a one‐dimensional chain structure, and complex 2 does a zero‐dimensional one. These three complexes further generate a three‐dimensional supramolecular architecture via strong hydrogen bonding interactions and packing interactions. These three metal coordination complexes show high catalytic performance for green synthesis of a variety of 3,4‐dihydropyrimidin‐2(1H)‐ones through the Biginelli reactions, which show several advantages such as excellent yields, short reaction times, eco‐friendly synthesis conditions, and simple isolated workup procedure. Interestingly, the order of catalytic activities for these catalysts is the following: 3>1>2, which can be ascribed to the acidities and hydrophobic interactions of phenyl sulfonate groups.

Are free radicals actually responsible for enhanced oxidation of contaminants by Cr(VI) in the presence of bisulfite?

Recently, the technology for the remediation of Cr(VI) pollutant via bisulfite has been found to be effective for fast elimination of co-contaminants especially in acidic solution, where free radicals (i.e., sulfate and/or hydroxyl radicals) are proposed to act as dominant oxidants. Here, it was demonstrated that high-valent Cr intermediate played a primary role in the Cr(VI)/bisulfite system through applying methyl phenyl sulfoxide (PMSO) as a probe. PMSO was effectively transformed in the Cr(VI)/bisulfite system with appreciable generation of methyl phenyl sulfone (PMSO2) product, while PMSO was oxidized by free radicals to hydroxylated and/or polymeric products rather than PMSO2. The involvement of high-valent Cr species was further supported by the formation of 18O-labeled PMSO2 in 18O labeling experiments, where the incorporation of 18O from solvent water H218O into PMSO2 was likely resulted from competitive oxygen exchange of Cr-oxo species with water. The relative contribution of high valent Cr species versus free radicals was evaluated based on the yield of PMSO2, which was dependent on the solution chemistry such as [Cr(VI)]:[bisulfite] ratio and dissolved oxygen. This work advances the understanding of chromium chemistry involved in the Cr(VI)/bisulfite system. These findings have important implications on the application of this “waste control by waste” technology for environmental decontamination.

Quantitative evaluation of relative contribution of high-valent iron species and sulfate radical in Fe(VI) enhanced oxidation processes via sulfur reducing agents activation

Recently, it has been reported that sulfur reducing agents (e.g., sulfite and thiosulfate) can effectively activate Fe(VI), leading to a fast degradation of various contaminants. However, the reactive intermediates (i.e., high-valent iron species versus free radicals) involved in the Fe(VI)/sulfite and Fe(VI)/thiosulfate systems remain far from clear. In this work, by using methyl phenyl sulfoxide (PMSO) as a mechanistic probe, we quantitatively assessed the relative contribution of high-valent iron species versus sulfate radical in these two systems. High-valent iron species oxidized PMSO to methyl phenyl sulfone product (PMSO2), while sulfate radical oxidized PMSO to hydroxylated and/or polymeric products. The yield of PMSO2 (mole of PMSO2 formed per mole of PMSO consumed) was quantified to be in the range of 30–95% under various conditions. This finding suggested the contribution of both high-valent iron species and sulfate radical in the Fe(VI)/sulfite system, which was dependent on solution chemistry (i.e., solution pH and [Fe(VI)]:[sulfite] ratio). Comparatively, the yield of PMSO2 in the Fe(VI)/thiosulfate system remained as high as 90–100% under various conditions. This finding indicated that only high-valent iron species was involved in the Fe(VI)/thiosulfate system and the contribution of sulfate radical was negligible. The discrepancy in the effects of oxygen, alcohol scavenger and co-existing components (e.g., Cl−, HCO3−, and humic acid) on the Fe(VI)/sulfite versus Fe(VI)/thiosulfate systems also indicated the involvement of different oxidants in these two systems.

Synthesis, Structure, and Chemical Transformations of 2-Chloroprop-2-en-1-yl Sulfones

A green approach was proposed for the synthesis of 2-chloroprop-2-en-1-yl sulfones in 47–94% yield. The molecular and crystal structures of 2-chloroprop-2-en-1-yl phenyl sulfone and 2-chloroprop-2-en-1-yl methyl sulfone were determined by X-ray analysis. π-Stacking interaction between the benzene ring and double bond was revealed in the crystal structure of 2-chloroprop-2-en-1-yl phenyl sulfone. Chloropropenyl sulfones were found to readily undergo dehydrochlorination to give stable allenyl sulfones and alkaline hydrolysis to produce the corresponding acetonyl sulfones. The latter can be converted to oximes by treatment with hydroxylamine hydrochloride.

Amide derivatives of 3-aminopropylsilatrane

Silatranes bearing an amide group in the axial chain have been synthesized by the reaction of 1-(3-aminopropyl)silatrane with arylchalcogenylacetic acids (Het)ArYCH2CO2H [(Het)Ar = 2-MeC6H4, 4-Cl-2-MeC6H3, 4-ClC6H4, 3-indolyl; Y = O, S], and their structures have been established by 1H,13C, 15N, 29Si NMR and IR spectroscopy. When 4-chlorophenylsulfonylacetic acid was employed, the reaction proceeded unexpectedly via the 4-chlorophenyl methyl sulfone intermediate and resulted in methyl 4-[3-(1 silatranyl)propylamino]phenyl sulfone.

Catalytic oxidation of contaminants by Fe0 activated peroxymonosulfate process: Fe(IV) involvement, degradation intermediates and toxicity evaluation

In this study, the catalytic degradation of atrazine (ATZ) by peroxymonosulfate (PMS) activated with commercial Fe0 was investigated under different pH conditions. The degradation process was pH dependent, among which acidic and neutral conditions favored Fe0 corrosion and PMS decomposition. Electron spin resonance (ESR) tests and alcohol quenching experiments confirmed the simultaneous presence of sulfate radical (SO4−) and hydroxyl radical (OH) in the Fe0/PMS system, both of which were quantified via indirect monitoring of the generation of benzoquinone (BQ) and p-hydroxybenzoic acid (HBA), respectively. In addition, ferryl ion (Fe(IV)) was identified to be involved in the Fe0/PMS system based on the selective transformation from methyl phenyl sulfoxide (PMSO) to methyl phenyl sulfone (PMSO2). Coupled with SEM and XPS results, the activation mechanism of the Fe0/PMS system was thought to be that Fe(II) released from Fe0 corrosion decomposed PMS into SO4− and OH or reacted with PMS to yield Fe(IV), accompanied by the final conversion of Fe(II) to Fe(III). Furthermore, possible degradation pathways were proposed according to intermediates detected by LC-MS, and dechlorinated and dealkylated byproducts were quantitatively analyzed. Ultimately, toxicity tests based on luminescent bacteria Vibrio qinghaiensis sp.-Q67 suggested the detoxification of ATZ by the Fe0/PMS system.

OIL-IN-WATER (O/W) EMULSIONABLE CONCENTRATE OF ISHPINK (Ocotea quixos) WITH THERMODYNAMIC STABILITY

ABSTRACT Ecuador has a vast number of native species with fungicidal, herbicidal, and insecticidal properties, of which several have been studied; however, few plant species have been applied for the development of commercial products. Ocotea quixos is an indigenous plant of the Ecuadorian Amazon that has fungicidal properties. In this work, we focus on developing an emulsifiable concentrate that is physically stable for use in the agricultural industry. The study aimed to determine the appropriate formulation to prepare an emulsifiable concentrate with thermodynamic stability. For the formulation, we used Ocotea quixos essential oil with cinnamaldehyde as an active ingredient, with solvesso 100 as the solvent, two non-ionic emulsifiers (Span-20 and Tween-20), and calcium phenyl sulfonate as an anionic emulsifier to obtain a stable product. The results showed that the OC5C emulsifiable concentrate has the best stability characteristics with the hydrophilic-lipophilic balance (HLB) within the range of 14 to 16 at room temperature as well as at high and low temperature with a drop size between 3 and 4 µm.

Effect of Irradiation on Hydrodynamic Properties of Extraction Mixtures Based on Carboxylic Acid Diamides in FS-13 Diluent

The hydrodynamic properties of three promising extraction mixtures, 0.05 M solutions of 2,2′-bi-pyridine-6,6′-dicarboxylic acid di(N-ethyl-4-hexylanilide) (DYP-7), 2,6-pyridinedicarboxylic acid di(N-ethyl-4-fluoroanilide) [Et(pFPh)DPA)], and 2,2′-bipyridine-6,6′-dicarboxylic acid di(N-ethyl-4-ethylanilide) (DYP-9) in trifluoromethyl phenyl sulfone (FS-13), were studied. The density, viscosity, surface tension, and settling rates in the steps of nitric acid extraction, stripping, and regeneration with sodium carbonate solutions were determined for these systems before and after the action of ionizing radiation. The concentrations of the extrac-tants in the irradiated samples were determined, and the radiation-chemical yields of their decomposition were calculated. The density and surface tension increase upon irradiation to a dose of 100 kGy but decrease upon further irradiation.

Effect of chelators on the production and nature of the reactive intermediates formed in Fe(II) activated peroxydisulfate and hydrogen peroxide processes

Iron chelators are often used to improve the performance of Fe(II) activated peroxides (e.g., peroxydisulfate (PDS) and hydrogen peroxide (H2O2)) for oxidative water treatment over a wide pH range due to the enhanced solubility of iron in the presence of chelators at high pH. In this study, we compared the effect of various chelators on the production and nature of the reactive intermediate formed in Fe(II)/PDS and Fe(II)/H2O2 systems by using methyl phenyl sulfoxide (PMSO) as a probe, which could distinguish ferryl ion (Fe(IV)) from free radicals (•OH and SO4•-) due to their marked difference in product formation. Six representative chelators (oxalate acid (OA), citric acid (CA), nitrilotriacetic acid (NTA), ethylenediaminetetraacetic acid (EDTA), pyrophosphate (PPP), and tetrapolyphosphate (TPP)) which covered the commonly used polycarboxylates, aminocarboxylates, and polyphosphates ligands were selected. In chelator assisted Fe(II)/PDS systems, the highest PMSO transformation efficiency at pH 3–9 was obtained in cases with polycarboxylates, due to their higher reactivity to PDS activation, lower steric hindrance, and stronger ability in promoting Fe(II)/Fe(III) cycle. Comparatively, in chelator assisted Fe(II)/H2O2 systems, TPP addition achieved the best performance in PMSO transformation at pH > 5. Moreover, the yield of Fe(IV) indicative product (methyl phenyl sulfone, PMSO2) decreased with increasing chelator/Fe(II) molar ratio, but was independent on pH in cases of PDS, indicating that chelator altered reactive intermediate nature from Fe(IV) to SO4•- and Fe(IV) yield was not sensitive to pH. In cases of H2O2, chelator decreased PMSO2 production while promoting PMSO loss at near-neutral pH, suggesting that Fe(II)-chelator complexes also tended to catalyze H2O2 to generate •OH rather than Fe(IV).

Proton Transport within Acid Aggregates in a Hydrated Precise Sulfophenylated Polyethylene

Hydrated acid aggregates in a precise sulfophenylated polyethylene exhibit high proton conductivity. This study focuses on a new precise polymer synthesized by ring-opening polymerization, p5PhSA, that has a polyethylene backbone with a sulfonated phenyl group pendant on every 5th carbon. The structure of p5PhSA is characterized with X-ray scattering and the proton conductivity is measured by electrical impedance spectroscopy. Experiments are performed as a function of relative humidity and temperature. Water uptake in p5PhSA is determined by sorption measurements as a function of humidity. Atomistic molecular dynamics simulations are used to elucidate the structure of the acid aggregates in the amorphous polymer matrix and are directly compared to absolute X-ray scattering data. At 40°C and 90% relative humidity, the proton conductivity of p5PhSA is 0.23 S/cm, exceeding that of Nafion at the same conditions. At room temperature, the interaggregate distance nearly doubles from 1.8 nm at 0% relative humidity to 3.4 nm at 100% relative humidity. The swelling of these acid aggregates with water is reversible and facilitates the proton transport through p5PhSA. Figure 1

Further understanding the involvement of Fe(IV) in peroxydisulfate and peroxymonosulfate activation by Fe(II) for oxidative water treatment

Very recently, we have interestingly found that the Fe(II)-activated peroxydisulfate (PDS) process can oxidize methyl phenyl sulfoxide (PMSO) to its oxygen transfer product methyl phenyl sulfone (PMSO2), suggesting the possible occurrence of a ferryl intermediate (Fe(IV)) rather than long recognized sulfate radical (SO4−) in this process. In this work, the formation of PMSO2 was also observed when PMSO was treated by the Fe(II)/peroxymonosulfate (PMS) system over the pH range of 3–7, and the yield of PMSO2 (i.e., the molar ratio of PMSO2 formed to PMSO lost) was quantified to be approximately 100% under acidic conditions, similar to the Fe(II)/PDS system. Moreover, 18O from isotope-labeled water (H218O) was successfully incorporated into PMSO2 product when PMSO was oxidized by the Fe(II)/PDS and Fe(II)/PMS systems in H218O, likely due to the competitive oxygen exchange of Fe(IV)-oxo species with H218O. Further, Fe(IV) evolution profiles in both systems were predicted by a Fe(IV)-mediated kinetic model, and these results are in good agreement with the experimental data obtained with a stopped-flow spectrophotometer.