Ethyl Sulfone Research Articles

Rare-Earth Metal-Organic Framework with Nonplanar Porphyrin Groups for High-Efficiency Photocatalysis.

Nonplanar porphyrins play crucial roles in many biological processes and chemical reactions as catalysts. However, the preparation of artificial nonplanar porphyrins suffers from complicated organic syntheses. Herein, we present a new rare-earth porphyrinic metal-organic framework (RE-PMOF), BUT-233, which is a three-dimensional (3D) framework structure with the flu topology consisting of 4-connected BBCPPP-Ph ligands H4BBCPPP-Ph = 5',5⁗-(10,20-diphenylporphyrin-5,15-diyl)bis([1,1':3',1″-terphenyl]-4,4'' dicarboxylic acid) and 8-connected Eu6 clusters. Noteworthily, the porphyrin cores of the BBCPPP-Ph ligands in BUT-233 are nonplanar with a ruffle-like conformation. In contrast, the porphyrin core in the free ligand H4BBCPPP-Ph is in a nearly ideally planar conformation, as confirmed by its single-crystal structure. BUT-233 is microporous with 6-8 Å pores and a Brunauer-Emmett-Teller (BET) surface area of 649 m2/g, as well as high stability in common solvents. The MOF was used as a photocatalyst for the oxidation degradation of a chemical warfare agent model molecule CEES (CEES = 2-chloroethyl ethyl sulfide) under the light-emitting diode (LED) irradiation and an O2 atmosphere at room temperature. CEES was almost completely converted into its nontoxic light-oxidized product CEESO (CEESO = 2-chloroethyl ethyl sulfoxide) in only 5 min with t1/2 = 2 min (t1/2: half-life). Moreover, the toxic deep-oxidized product 2-chloroethyl ethyl sulfone (CEESO2) was not detected. The catalytic activity of BUT-233 was high in comparison with those of some previously reported MOF catalysts. The results of photo/electrochemical property studies suggested that the high catalytic activity of BUT-233 was benefited from the presence of nonplanar porphyrin rings on its pore surface.

Targeting carbonic anhydrases II/IX/XII with novel series of coumarin-based compounds: Synthesis, biological activity and molecular dynamics analysis

In the current study, unique series of coumarin sulfonate and sulfamate derivatives were synthesized. Their selectivity and inhibitory activity against glaucoma and cancer-associated CAs (hCA II, IX, and XII) were evaluated compared to standard acetazolamide. In addition, the cytotoxic effects of the synthesized compounds on colorectal carcinoma (HCT116) were examined. Generally, structure-activity relationship (SAR) analysis revealed that potent inhibitors bearing zinc binding group (ZBG) dimethyl sulfamate (4a-c) were shown to lack selectivity against three isoforms owing to the classical inhibitory mode of action. The incorporation of aryl or fluoro aryl sulfone moiety in non-sulfamate coumarin derivatives shifted selectivity toward cancer-related isoforms XII and IX, respectively. Para-fluorine substituted derivative 3c with IC50 value of 0.62 µM exhibited excellent activity and selectivity against hCA IX, while benzene sulfone possessing derivative 3b demonstrated selectivity toward hCA XII with IC50 value of 0.56 µM. Moreover, coumarin derivatives with ethyl sulfone (3e, 3i, and 6a) reported excellent selectivity toward CAII. In-silico studies were also conducted over selective, potent compounds. Molecular docking studies have shown that potent compounds could interact with the active site by different modes of action. The molecular dynamic analysis confirmed the stability of the protein in the presence of a potent ligand.

Photocatalytic Use of Porphyrin Based Functional Materials

Porphyrin-containing materials have been often used in photocatalysis for chemical transformations such as hydrogen evolution, CO2 reduction, purification, sterilization, and photoelectrochemical conversion. Reactive oxygen species (ROS) including free radicals/electrons and singlet oxygen (1O2) generated by photosensitizers are known to undergo secondary reactions such as multiple organic transformations and degradation of a wide variety of contaminants. Specially, they are often used for decomposition of chemical warfare agents (CWAs) such as sulfur mustard gas, which is one of the most notorious and effective chemical weapons. Various photocatalysts have been developed with successful use of ROS in photooxidation reactions. For example, in photodegradation of 2-chloroethyl ethyl sulfide (2-CEES), a sulfur mustard simulant, and demonstrated a selective decomposition to 2-chloroethyl ethyl sulfoxide (2-CEESO). Note that overoxidation of 2-CEESO generates 2-chloroethyl ethyl sulfone (2-CEESO2, fully oxidized product) and becomes a highly toxic material. Therefore, selective oxidation of 2-CEES without generating 2-CEESO2 is considered an important process in the detoxification of sulfur mustard gas.In this presentation, photocatalytic application of porphyrin based materials including PIM, silica, MOF and nanofiber will be demonstrated. Although porphyrins are well-known photosensitizers for effective photocatalytic reactions, they often suffer from self-degradation. Incorporation of porphyrins into nano materials may prevent self-degradation, resulting in effective systems with a long lifetime.

Hot pad–batch dyeing of cotton fabrics using reactive blue-vinyl sulfone dye

Cold pad–batch dyeing of reactive dyes is low energy consumption and a clean dyeing technique. However, the room dyeing temperature requires strongly active base reactive dyes for dye fixation, bringing about the limitation of dye adaptability. Here, we propose a new technology of hot pad–batch dyeing that has the advantages of higher dye fixation and excellent color fastness. Three blue reactive dyers (C.I. Reactive Blue 19, C.I. Reactive Blue 21, C.I. Reactive Blue 203) that contain β-sulfate ethyl sulfone were used to increase the dye fixation of reactive dyes with cotton fibers. The effects of alkali concentration, dyeing temperature, batching time, and salt concentration on the dyeing performance of cotton fabrics were studied. The effects of post-treatment (soaping and fixation) on the K/ S values and color fastness were also investigated. The study showed that the dye fixation rate of the three reactive blue dyes was higher than 87%, and the rubbing and washing color fastness was more than grade 3–4 in the process of hot pad–batch dyeing of cotton fabrics. Furthermore, the dyed cotton fiber was fixed with a fixing agent (polyurethane (PU) and a mixture of PU and an aziridine crosslinker), and the color fastness reached not less than grade 4. Compared with cold pad–batch dyeing, hot pad–batch dyeing has the advantages of higher dye fixation and excellent color fastness for the three reactive blue dyes. Therefore, the dyeing performance of β-sulfate ethyl sulfone types of blue reactive dyes using hot pad–batch dyeing can effectively reduce the burden of post-treatment and the discharge of dyeing wastewater, and has a good application prospect in the dyeing of cotton fabrics.

Target and nontarget screening of PFAS in drinking water for a large-scale survey of urban and rural communities in Québec, Canada

Limited monitoring data are available regarding the occurrence of emerging per- and polyfluoroalkyl substances (PFAS) in drinking water. Here, we validated an analytical procedure for 42 PFAS with individual detection limits of 0.001–0.082 ng/L. We also evaluated how different sample pH conditions, dechlorinating agents, and storage holding times might affect method performance. PFAS were analyzed in tap water samples collected at a large spatial scale in Quebec, Canada, covering 376 municipalities within 17 administrative regions. Target and nontarget screening revealed the presence of 31 and 23 compounds, respectively, representing 24 homolog classes. Overall, 99.3% of the tap water samples were positive for at least one PFAS, and the ƩPFAS ranged from below detection limits to 108 ng/L (95th percentile: 13 ng/L). On average, ƩPFAS was 12 times higher in tap water produced from surface water than groundwater; however, 6 of the top 10 contaminated locations were groundwater-based. Perfluorooctanoic acid (PFOA) and perfluorooctane sulfonate (PFOS) had high detection rates (88% and 80%, respectively). PFOS (median: 0.15 ng/L; max: 13 ng/L) and PFOA (median: 0.27 ng/L; max: 8.1 ng/L) remained much lower than current Health Canada guidelines but higher than USEPA's interim updated health advisories. Short-chain (C3-C6) perfluoroalkyl sulfonamides were also recurrent, especially the C4 homolog (FBSA: detection rate of 50%). The 6:2 fluorotelomer sulfonyl propanoamido dimethyl ethyl sulfonate (6:2 FTSO2PrAd-DiMeEtS) was locally detected at ∼15 ng/L and recurred in 8% of our samples. Multiple PFAS that are most likely to originate from aqueous film-forming foams were also reported for the first time in tap water, including X:3 and X:1:2 fluorotelomer betaines, hydroxylated X:2 fluorotelomer sulfonates, N-trimethylammoniopropyl perfluoroalkane sulfonamides (TAmPr-FHxSA and TAmPr-FOSA), and N-sulfopropyl dimethylammoniopropyl perfluoroalkane sulfonamidopropyl sulfonates (N-SPAmP-FPeSAPS and N-SPAmP-FHxSAPS).

Sequential treatment of simulated textile wastewater using zero-valent aluminum under alkaline conditions and biodegradation

The azo dye reactive yellow 145 (RY145) is inherently recalcitrant due to the presence of azo, ethyl sulfone and monochlorotriazine groups. This study explored removal of RY145 using zero valent aluminum (ZVAl) treatment under alkaline conditions followed by aerobic degradation using the bacterial strains Pseudomonas aeruginosa (RS1) and Thiosphaera pantotropha. During pretreatment using 1 g L−1 ZVAl at pH 11, 59% decolorization was observed after 30 min for 50 mg L−1 dye. However, even after carbon source supplementation, the supernatant could not support microbial activity due to the high aluminum concentration in solution at pH 11. After pH adjustment to neutral and Al(OH)3 precipitation, complete decolorization occurred and subsequently microbial degradation of the intermediates could be achieved. ZVAl pretreatment followed by biological treatment could cause an overall TOC reduction of 65% within 96 h. Sorption of dye on the precipitate only contributed to 13% dye removal. The bacterial cultures could utilize nitrogen from the dye intermediates formed after alkaline ZVAl treatment. The sequential treatment also reduced the concentration of total amines and phytotoxicity to Vigna radiata seeds. When a simulated textile wastewater containing 200 mg L−1 of RY145 was subjected to this sequential treatment, complete dye decolorization and 99.2% overall TOC reduction was observed in 30.5 h. The other compounds present in the synthetic wastewater facilitated decolorization as well as mineralization of the dye.

Use of porphyrin-containing polymers of intrinsic microporosity as selective photocatalysts for oxidative detoxification of chemical warfare agent simulant

Porphyrin-based polymers of intrinsic microporosity (PIMs) in photocatalytic degradation of a mustard-gas simulant (2-chloroethyl ethyl sulfide (2-CEES)) was demonstrated. Under blue-ultraviolet (UV) light-emitting diode (LED) irradiation, porphyrin-based PIMs PP-H2 and PP-Zn(II) worked as effective heterogeneous photocatalysts for oxidation of 2-CEES. Solvent played an important role in the conversion and selectivity of 2-CEES oxidation. When AcCN was used as a solvent, PP-H2 and PP-Zn(II) demonstrated complete conversion of 2-CEES in 30 and 50 min, respectively, whereas they showed complete conversion at 60 and 70 min, respectively, when MeOH was used as a solvent. Moreover, these PIMs produced 2-chloroethyl ethyl sulfoxide (2-CEESO) as a major product with small amounts of 2-chloroethyl ethyl sulfone (2-CEESO[Formula: see text], ethyl methoxyethyl sulfoxide (EMSO), and vinyl sulfoxide (EVS) as side products in most solvents. However, when MeOH was used as a solvent, highly toxic 2-CEESO2 was not observed as a side product. Furthermore, these PIMs showed no significant changes in photocatalytic activity even after five cycles of reuse, indicating their high stability. Thus, the series of PIMs prepared herein can perform well as heterogeneous catalysts in photooxidation of 2-CEES under blue-UV LED light, with PP-H2 being the most effective oxidation catalyst, leading to fast conversion and high selectivity.

Chemical warfare agents decontamination via air mircoplasma excited by a triboelectric nanogenerator

Low-temperature air plasma, as an emerging green and efficient technology, has great potential to do chemical warfare agents (CWAs) decontamination. However, conventional plasma devices are bulky, costly and inconvenient. More importantly, their practical application is limited by the power grid and battery capacity. Here, A double layer paper-strip rotary triboelectric nanogenerator (dps-rTENG) is fabricated to serve as a self-powered high-voltage device to induce microplasma in air for CWAs decontamination. The degradation efficiency of 2-chloroethylethyl sulfide (2-CEES), a surrogate for the sulfur mustard (HD), reaches more than 99% within 2 min of microplasma treatment, and the energy utilization efficiency (Ee) of the dps-rTENG is calculated to be 0.520 μg/J, which is one order of magnitude higher than those of the commercial power supplies. Further study confirms that the degradation process of the dps-rTENG induced microplasma is well controllable to avoid the formation of large amounts of 2-chloroethyl ethyl sulfone (2-CEESO2), a toxic excessive oxidation product. Triboelectric microplasma provides a new approach for self-powered, easily portable decontamination system for CWAs in future.

Isomeric sp2-C-conjugated porous organic polymer-mediated photo- and sono-catalytic detoxification of sulfur mustard simulant under ambient conditions

Isomeric sp2-C-conjugated porous organic polymer-mediated photo- and sono-catalytic detoxification of sulfur mustard simulant under ambient conditions

Decontamination of 2-Chloroethyl ethyl sulfide on the surface by atmospheric pressure plasma jet

Atmospheric pressure plasma jet (APPJ) were used to decontaminate the surface’s 2-Chloroethyl ethyl sulfide (2-CEES), a kind of sulfur mustard (HD) simulant. The power of the APPJ device didn’t exceed 7.77 W. Helium APPJ was easier to generate plasma jet than argon APPJ. The treated nude mouse skin surface’s temperature slowly reached 30.4 °C and no obvious lesions in the dermis and skin appendages after 15 min treatment. Compared with argon APPJ, the helium APPJ produced more ·OH and the maximum concentration of ·OH was 3.748 × 10−9 mol/L. Attributed to the low density and more ·OH content, the helium APPJ had a better decontamination effect. With a maximum voltage of 7 kV and a helium flow rate of 4 L/min, 2-CEES (4.53 mg/cm2) can be completely decontaminated in 2.5 min, and no gaseous 2-CEES was detected. The detection of the 2-Hydroxyethyl ethyl sulfide proved the role of ·OH in the reaction system. During the reaction, 2-Chloroethyl ethyl sulfoxide and 2-Chloroethyl ethyl sulfone were also detected. The plasma jet could reduce the toxicity by destroying the parent molecule (2-CEES) in a short time, but it took more time to eliminate the intermediate products. No relevant intermediate products were detected in the gaseous, ensured the safety of personnel operating in open spaces.

Synthesis and characterization of novel fluorescent reactive dyes for dyeing of cotton fabrics

Nowadays, fluorescent reactive dyes have limited color shades and brilliance; thus, they are a group of colorants in the textile industry for dyeing of cotton fabric with high demand. This research has designed and synthesized two novel fluorescent reactive dyes based on fluorescein. In this respect, 4,4′-diaminostilbene-2,2′-disulfonic acid and 4-aminophenyl-4-β-hydroxyl ethyl sulfone sulfate ester reacted with the cyanuric chloride, separately. Then those were reacted with fluorescein and obtained two reactive dyes D1 with dual-emission wavelength and D2 with an emission spectrum. The characterizations of two dyes were carried out using the TLC, 1HNMR, 13CNMR, FTIR, elemental analysis, Ultra-violet spectra, and Fluorimeter techniques. The absorption and emission parameters of dyes in solutions were obtained. The result indicated that the parameters of D1 were more than D2. The results showed that two dyes had a positive solvatochromism effect. The synthesized dyes were applied on cotton fabric, and their color characteristics, fixation and exhaustion percentage were studied.

Iodine-catalyzed sulfuration of isoquinolin-1(2H)-ones applying ethyl sulfinates

Sulfuration of isoquinolin-1(2H)-ones at the C-4 position by employing ethyl sulfonates.

Catalytic oxidation/photocatalytic degradation of ethyl mercaptan on α-MnO2@H4Nb6O17-NS nanocomposite

Ethyl mercaptan, which is prevalent in biogas and natural gas, must be removed to a lower level because of its toxic, odorous and corrosive characteristics. Herein, a novel α-MnO2@H4Nb6O17-NS nanocomposite was fabricated by co-precipitation process for the removal of ethyl mercaptan. The compositions, structures, morphologies and properties of the as-prepared samples were characterized in detail by a combination of power X-ray diffraction, laser Raman spectroscopy, transmission electron microscopy, elemental mapping, UV–visible absorption spectrum and N2 adsorption-desorption measurements. The H4Nb6O17 nanoscroll was modified by α-MnO2 nanoparticles clearly enhanced the catalytic oxidation and photocatalytic degradation activity for ethyl mercaptan under visible light. The α-MnO2 phase provides the main active sites and the ethyl mercaptan was decomposed into diethyl sulfides and ethyl sulfonates. Finally, a possible mechanism for the removal of ethyl mercaptan was proposed.

Oxidation of diethyl disulfide with atmospheric oxygen in the presence of 1,3-dimethylimidazolium dimethyl phosphate

Oxidation of diethyl disulfide with atmospheric oxygen at 363 К in the presence of 1,3-dimethylimidazolium dimethyl phosphate is described. On the basis of the 1Н, 31Р, and 13С NMR data, it is shown that oxidation of diethyl disulfide results in ethyl sulfonates. Formation of ethyl alcohol, which is a product of a side reaction of ethyl sulfonate hydrolysis, probably, catalyzed by the 1,3-dimethylimidazolium cation, was detected using HPLC and 1Н and 13С NMR.

A catalyst-free process for gas ozonation of reduced sulfur compounds

The feasibility of homogenous gas ozonation process was investigated in order to reduce the negative environmental impact caused by reduced sulfur compounds (RSCs). Emitted from a variety of industrial plants, this class of compounds are known by their odor properties. Selecting hydrogen sulfide (H2S), methyl ethyl sulfide (MES) and dimethyl disulfide (DMDS) as representative odorous RSCs, the influence of four gas ozonation process parameters (ozone concentration, humidity level, reactor temperature and residence time) on their removal efficiencies was evaluated using a Doehlert experimental design in an experimental domain compatible with industrial constraints. Ozone concentration was the only process parameter that has resulted in a positive – but limited – effect on the removal efficiency of the mix of RSCs. However, even if ozone was present in large excess (20 times the RSCs concentration), MES and DMDS were slightly consumed (around 30%). Only H2S has shown interesting removal efficiencies (up to 80%). In addition to the measurement of reagent concentrations, Selected Ion Flow Tube coupled with Mass Spectrometry (SIFT/MS) was applied to identify and quantify the potential products of RSCs-ozone reaction. Methyl ethyl sulfone (MESO2) was found to be the primary product of MES, whereas methyl methanethiosulfinate (DMSOS) and sulfur dioxide (SO2) for DMDS, suggesting that the organic monosulfide and disulfides would not follow the same reaction mechanism with ozone in gas phase. In addition, SO2 and H2O may not be the only end products for H2S ozonation, since additional peaks were detected in SIFT/MS spectra.

Detoxification of a Mustard-Gas Simulant by Nanosized Porphyrin-Based Metal–Organic Frameworks

Selectivity control of the decomposition of sulfur mustard (bis(2-chloroethyl)sulfide) under photo-oxidation conditions using molecular oxygen remains a challenge. In this work, the photo-oxidation of a mustard-gas simulant, 2-chloroethyl ethyl sulfide (CEES), was studied using porphyrin-based metal–organic framework (Por-MOFs) catalysts. It is shown that Por-MOFs are selective oxidizing agents in the transformation of CEES into 2-chloroethyl ethyl sulfoxide (CEESO) without the formation of the highly toxic sulfone product 2-chloroethyl ethyl sulfone (CEESO2). This method to detoxify mustard gas is regarded as more realistic, convenient, and effective than the other available methods.

Precision Sulfonic Acid Polyolefins via Heterogenous to Homogenous Deprotection

AbstractPolyolefins containing precisely spaced sulfonic acid functionality are made. First, precision ethyl sulfonate ester diene monomers are synthesized, which then are converted to acyclic diene metathesis polymers using Grubbs' catalysis. Subsequently, the poly(ethyl sulfonate esters) are deprotected post‐polymerization via two successful routes, both using a concept of “heterogenous to homogenous deprotection.” The resulting poly(sodium sulfonate) salts are then converted to precise poly(sulfonic acids), where the sulfonic acid functionality is placed either at every ninth or 21st carbon. For comparison, random versions of poly(sulfonates), their salts, and sulfonic acid polymers are synthesized via copolymerization of the “9” sulfonate monomer with 1,9‐decadiene. Precision placement of sulfonic acid functionality could lead to materials of potential utility.

Rapid Immobilization of Cellulase onto Graphene Oxide with a Hydrophobic Spacer

A rapid immobilization method for cellulase was developed. Functional graphene oxide was synthesized and grafted with hydrophobic spacer P-β-sulfuric acid ester ethyl sulfone aniline (SESA) though etherification and diazotization. The functionalized graphene oxide was characterized by Fourier-transform infrared spectroscopy and was used as the carrier for the immobilization of cellulase via covalent binding. The immobilization of cellulase was finished in a very short time (10 min) and very high immobilization yield and efficiency of above 90% were achieved after optimization. When compared with the free cellulase, thermal and operational stabilities of the immobilized cellulase were improved significantly. At 50 °C, the half-life of the immobilized cellulase (533 min) was six-fold higher than that of the free cellulase (89 min). Additionally, the affinity between immobilized cellulase (Km = 2.19 g·L−1) and substrate was more favorable than that of free cellulase (Km = 3.84 g·L−1), suggesting the immobilized cellulase has higher catalytic efficiency. The possible immobilization mechanism was proposed. The results strongly indicate that the immobilization is highly efficient and has great potential for the immobilization of other enzymes.

Effects of alkyl ethyl sulfonate dosage on cotton defoliation efficacy sprayed by UAV

Abstract: As a new low volume sprayer, unmanned aerial vehicle (UAV) application is developing quickly worldwide. Alkyl ethyl sulfonate soluble concentrate is a kind of spray adjuvants for defoliants, which is widely used in cotton defoliant application. The aim of this study was to compare the droplet deposition, defoliation and boll opening of a UAV added with six dosages of alkyl ethyl sulfonate on the cotton. Addition with 4.2 g a.i./hm 2 (one-sixtieth of the recommended dosage in the field) alkyl ethyl sulfonate could significantly increase the droplets coverage rate, and improve defoliation and boll opening effects. Added with lower dosage alkyl ethyl sulfonate (4.2 g a.i./hm 2 and 8.4 g a.i./hm 2 ), the droplet distribution uniformity was much better than that of moderate (84 g a.i./hm 2 ) and high dosage (252 a.i./hm 2 ) of alkyl ethyl sulfonate. It could not only ensure the effects of defoliation and boll opening, but also reduce the environmental pollution by alkyl ethyl sulfonate. Keywords: defoliant, alkyl ethyl sulfonate dosage, droplet deposition, unmanned aerial vehicle DOI:  10.33440/j.ijpaa.20190202.33.  Citation: Xiao Q G, Du R, Zhou T T, Han X Q, Wang G B, Fu W. Effects of alkyl ethyl sulfonate dosage on cotton defoliation efficacy sprayed by UAV.  Int J Precis Agric Aviat, 2019; 2(2): 67–75.

Supramolecular Design of Cellulose Hydrogel Beads

In the present study, we report the supramolecular design of cellulose-sulfonate hydrogel beads by blending water soluble sodium cellulose ethyl sulfonate (CES) with the pretreated cellulose in sodium hydroxide-ureawater solvent system at −6 °C followed by coagulation in the 2M sulfuric acid system. The increasing of CES amount from 10% to 90% had a substantial effect on the viscosity and storage (G′) and loss (G″) moduli of the blended solutions. The CES concentration up to 50% in blends led to the formation of physically stable hydrogels after coagulation in acidic medium at pH-1 and showed the retention of nearly the same CES concentration at pH-6 after continuous water washings. The increased sulfonate content also enhanced the water holding capacity and internal porosity of the beads. Both ATR-FTIR and Raman spectrometry were used for the qualitative determination of sulfonate groups and SEM-EDX was used for the quantitative estimation in dried beads. In this research, we have established a correlation between the presence of anionic charge in the polysaccharide blend and stability of the prepared hydrogel beads. Hence our research provides a systematic methodology to design functional, highly porous cellulose hydrogels having the potential to be tested further in biomedical and healthcare applications.