Regioselective 1,4-/1,3-Difunctionalization of 1,3-Enynes with Selenosulfonates in Water.

1,4-/1,3-Regioselective bifunctionalization of 1,3-enynes with selenosulfonates in water under catalyst-free conditions for the construction of sulfonyl allene and 1,3-disulfonyl-conjugated dienes respectively have been developed. The reactions feature mild reaction conditions in aqueous solution and remarkable regioselectivity controlled by substrates.

Copper-Catalyzed Chemoselective Coupling of N-Dithiophthalimides and Alkyl Halides: Synthesis of Unsymmetrical Disulfides and Sulfides.

In this paper, we report an unprecedented copper-catalyzed disulfides or sulfides coupling reaction involving unactivated alkyl halides and N-dithiophthalimides. This reaction can be conducted under mild conditions using low-cost metal catalysts and exhibits high chemical selectivity and functional group compatibility, enabling the efficient assembly of various sulfides and disulfides.

Visible Light-Catalyzed Reactions of Polysulfide (DBSPS) with Aryldiazonium.

A visible light-catalyzed radical coupling reaction of polysulfide reagents with aryldiazonium was developed, which gave thiosulfonates under mild conditions. In this reaction, the thiosulfonates were isolated in good yields with a broad tolerance to functional groups. And the synthesis of diaryl monosulfides were achieved through a step-by-step reaction of two molecular aryldiazonium with DBSPS, where the sulfur source was provided by DBSPS. It was worth noting that the reaction of this monosulfides could also be achieved by a one pot two-step process. The described polysulfide reagents were able to produce three new radicals: sulfonyl radicals, sulfur-sulfonyl radicals and sulfur-sulfur-sulfonyl radicals.

Dialdehyde cellulose (DAC) and polyethyleneimine (PEI) coated polyvinylidene fluoride (PVDF) membrane for simultaneously removing emulsified oils and anionic dyes.

Developing high-efficiency membrane for oil and dye removal is very urgent, because wastewater containing them can cause great damage to human and environment. In this study, a coated membrane was fabricated by applying DAC and PEI onto the commercial PVDF microfiltration membrane for supplying the demand. The coated membrane presents superhydrophlic and superoleophobic properties with a water contact angle of 0o and underwater oil contact angle exceed 150°, as well as excellent low underwater oil adhesion performance. The coated membrane shows high separation efficiency exceeded 99.0% and flux 350.0 L·m-2·h-1 when used for separating for six kinds of oil including pump oil, sunflower oil, n-hexadecane, soybean oil, diesel and kerosene in water emulsions. Additionally, the coated membrane can effectively remove anionic dyes, achieving rejection rates of 94.7%, 93.4%, 92.3%, 90.7% for the CR, MB, RB5, AR66, respectively. More importantly, the membrane was able to simultaneously remove emulsified oil and soluble anionic dyes in wastewater containing both of them. Therefore, this novel coated membrane can be a promising candidate for treating complex wastewater.

Regioselective Thiol-yne Reaction of Thiol with ((Methyl-d3)sulfonyl)ethyne: Synthesis of (2-((Methyl-d3)sulfonyl)vinyl)sulfides.

Herein, we have developed a new method for the synthesis of ((methyl-d3)sulfonyl)ethyne, which is cost-effective and environmentally friendly and can be synthesized at the gram level. As an ideal thiol-yne reagent, it can be reacted with various types of thiols to afford (Z)- and (E)-type vinyl sulfides under different conditions with high selectivity. In addition, it can complete the conformational transition from Z- to E-type products under suitable conditions, and can also carry out further derivatization smoothly. The deuterium content of all products was greater than 99%. The preliminary mechanistic studies support the visible light-mediated radical course, and herein provide a novel and efficient synthetic strategy for the direct introduction of deuterated methyl groups, enriching the methods for the construction of C-S bond-containing compounds.

Simultaneous Preparation of Sulfides/Selenides and Sulfones via Synergistic Nickel-Catalyzed Reductive Coupling and SN2 Reaction.

Sulfone compounds and thioether compounds are two highly valuable classes of compounds, but it is challenging to prepare sulfone and thioether compounds simultaneously and efficiently. Here we report that sulfides/selenides and sulfones can be obtained simultaneously using allyl bromide/benzyl bromide-activated alkyl bromides and thiosulfonates/selenosulfonates using a nickel-catalyzed reductive coupling and SN2 synergistic strategy, which is characterized by excellent atom and step economy, mild reaction conditions, broad functional group compatibility, and excellent yields.

Nickel-Catalyzed Acid Chlorides with Tetrasulfides for the Synthesis of Thioesters and Acyl Disulfides.

Herein, we report a novel method for the synthesis of thioesters and acyl disulfides via nickel-catalyzed reductive cross-electrophile coupling of acid chlorides with tetrasulfides. This approach for the synthesis of thioesters and acyl disulfides is convenient and practical under mild reaction conditions, relying on easy availability. In addition, a wide range of thioesters and acyl disulfides were obtained in medium to good yields with good functional group tolerance. Moreover, thioesters and acyl disulfides can also be prepared at the gram scale, indicating that they have certain potential for industrial application.

Copper-Catalyzed Synthesis of S-S Bond-Containing Silanols from SCBs and Trisulfide-1,1-dioxides.

In this work, an efficient method for the copper-catalyzed ring-opening hydrolysis of silacyclobutanes to silanols was developed. This strategy has the advantages of friendly reaction conditions, simple operation, and good functional group compatibility. No additional additives are required in the reaction, and the S-S bond can also be introduced into the organosilanol compounds in one step. Furthermore, the success at the gram scale demonstrates the great potential of the developed protocol for practical industrial applications.

Synthesis of 1,3-Dibenzenesulfonylpolysulfane (DBSPS) and Its Application in the Preparation of Aryl Thiosulfonates from Boronic Acids.

Herein, we provide a novel method for the synthesis of 1,3-dibenzenesulfonylpolysulfane (DBSPS), which further reacts with boronic acids to afford thiosulfonates. Commercially available boron compounds greatly expanded the range of thiosulfonates. Experimental and theoretical mechanistic investigations suggested that DBSPS could provide both thiosulfone fragments and dithiosulfone fragments, but the generated aryl dithiosulfonates were unstable and decomposed into thiosulfonates.

Photoinduced Construction of Thieno[3,4-c]quinolin-4(5H)-ones/Selenopheno[3,4-c]quinolin-4(5H)-ones Using Diphenyl Disulfide or Diphenyl Diselenide as Sulfur or Selenium Sources.

A photocatalytic synthesis of thieno[3,4-c]quinolin-4(5H)-ones/selenopheno[3,4-c]quinolin-4(5H)-ones using diphenyl disulfide or diphenyl diselenide as sulfur or selenium sources was developed. Two C-S/Se bonds and one C-C bond were constructed simultaneously without transition metals and other additives.

Cu-catalyzed efficient construction of S (Se)-containing functional organosilicon compounds.

A Cu-catalyzed cascade reaction of four-membered silacyclobutanes (SCBs) and thiosulfonates to construct S (Se)-containing organosilicon compounds was developed. The protocol shows a wide range of substrate scope, high functional group compatibility and mild reaction conditions. New C-S (Se) and Si-O bonds were constructed in one step.

Hydrophilic and Positively Charged Polyvinylidene Fluoride Membranes for Water Treatment with Excellent Anti-Oil and Anti-Biocontamination Properties.

Membrane fouling limits the rapid development of membrane separations. In this study, a blend membrane containing polycationic liquid (P(BVImBr1-co-PEGMA1)) is presented that can improve the antifouling performance of polyvinylidene fluoride (PVDF) membranes. By mixing the polycationic liquid into PVDF, an improved membrane-surface hydrophilicity and enlarged membrane porosity were detected. The water contact angle decreased from 82° to 67°, the porosity enlarged from 7.22% to 89.74%, and the pure water flux improved from 0 to 631.68 L m-2 h-1. The blend membrane surfaces were found to be always positively charged at pH 3~10. By applying the membranes to the filtration of oil/water emulsion and bovine serum albumin (BSA) solution, they showed a very high rejection rate to pollutants in wastewater (99.4% to oil droplets and 85.6% to BSA). The positive membrane surface charge and the increased membrane hydrophilicity resulted in excellent antifouling performance, with the flux recovery rates of the dynamic filtration tests reaching 97.3% and 95.5%, respectively. Moreover, the blend membranes demonstrated very low BSA adhesion and could even kill S. aureus, showing excellent antifouling properties.

Highly Effective Anti-Organic Fouling Performance of a Modified PVDF Membrane Using a Triple-Component Copolymer of P(Stx-co-MAAy)-g-fPEGz as the Additive.

In this study, a triple-component copolymer of P(Stx-co-MAAy)-g-fPEGz containing hydrophobic (styrene, St), hydrophilic (methacrylic acid, MAA), and oleophobic (perfluoroalkyl polyethylene glycol, fPEG) segments was synthesized and used as an additive polymer to prepare modified PVDF membrane for enhanced anti-fouling performance. Two compositions of St:MAA at 4:1 and 1:1 for the additive and two blending ratios of the additive:PVDF at 1:9 and 3:7 for the modified membranes were specifically examined. The results showed that the presence of the copolymer additive greatly affected the morphology and performance of the modified PVDF membranes. Especially, in a lower ratio of St to MAA (e.g., St:MAA at 1:1 versus 4:1), the additive polymer and therefore the modified PVDF membrane exhibited both better hydrophilic as well as oleophobic surface property. The prepared membrane can achieve a water contact angle at as low as 48.80° and display an underwater oil contact angle at as high as 160°. Adsorption experiments showed that BSA adsorption (in the concentration range of 0.8 to 2 g/L) on the modified PVDF membrane can be reduced by as much as 93%. From the filtration of BSA solution, HA solution, and oil/water emulsion, it was confirmed that the obtained membrane showed excellent resistance to these organic foulants that are often considered challenging in membrane water treatment. The performance displayed slow flux decay during filtration and high flux recovery after simple water cleaning. The developed membrane can therefore have a good potential to be used in such applications as water and wastewater treatment where protein and other organic pollutants (including oils) may cause severe fouling problems to conventional polymeric membranes.

Smart Self-Cleaning Membrane via the Blending of an Upper Critical Solution Temperature Diblock Copolymer with PVDF.

Poly(2,2,2-trifluoroethyl methacrylate)-b-poly(imidazoled glycidyl methacrylate-co-diethylene glycol methyl ether methacrylate) (PTFEMA-b-P(iGMA-co-MEO2MA)) containing an upper critical solution temperature (UCST) polymer chain was prepared and blended with poly(vinylidene fluoride) (PVDF) to produce a thermoresponsive membrane with smart self-cleaning performance. The successful preparation of the membrane was demonstrated by attenuated total reflection-Fourier-transform infrared spectroscopy, X-ray photoelectron spectroscopy, and scanning electron microscopy characterization. The membrane shows UCST performance, and its flux changes with the filtrate temperature as the UCST polymer chain stretches out and contracts in response to various temperatures. In addition, the UCST polymer chain can disrupt the foulant and push it away from the membrane when the temperature is above the UCST and thus enables membranes to exhibit a smart self-cleaning behavior. To the best of our knowledge, this work is the first report of a smart self-cleaning membrane based on the blending of a diblock copolymer containing a UCST polymer chain with PVDF.

Enhancing the Antifouling Properties of Poly(vinylidene fluoride) (PVDF) Membrane through a Novel Blending and Surface-Grafting Modification Approach.

In this study, poly(vinylidene fluoride) (PVDF) membrane was modified through a novel approach by first blending an active component (poly(vinylidene fluoride-co-chlorotrifluoroethylene), P(VDF-co-CTFE)) with the PVDF base material, followed by surface grafting of the membrane on the active component to obtain a triblock copolymer functional structure. The prepared membranes were characterized by various analyses, including Fourier-transform infrared, X-ray photoelectron spectroscopy, atomic force microscopy, scanning electron microscope, and filtration tests. It was found that the modified membrane surface showed a much better hydrophilicity (water contact angle of 67.3°) and oleophobicity (oil contact angle of 129.7°). The modification reduced the average surface pore size (from 0.1495 to 0.1072 µm) and thus lowered the pure water flux (from 364.0 to 224.6 L m-2 h-1 at 0.10 MPa of transmembrane pressure), but significantly increased the relative flux recovery (RFR) and the retention efficiency of the modified membrane during the filtration of bovine serum albumin solution and oil/water emulsion. For example, the modified membranes showed 98.6% oil retention (at feed concentration of 0.4 g L-1), 92.7% RFR by simple water flushing after filtration, and a consistently high oil removal of 96% or above during a five-cycle-continuous filtration test, as compared to 30.4% oil retention and 51.8% RFR for unmodified PVDF/P(VDF-co-CTFE) blend membrane.