Upper-rim-modified thioether thiacalix[4]arene used for liquid-liquid extraction of Au(Ⅲ)and Pd(Ⅱ)in hydrochloric acid medium

Gold(Au)and palladium(Pd)play an increasing role in the production and human life;Therefore,it is of great significance to study their recovery.A 5,11,17,23-tetra-ethylthio-25,26,27,28-tetra-hydroxyl thiacalix[4]arene(TCAET)was synthesized specifically for the capture of Au(Ⅲ)and Pd(Ⅱ)from HCl medium by liquid-liquid extraction.In a 0.1 mol·L^(-1)HCl medium,the transfer of Au(Ⅲ)and Pd(Ⅱ)from the aqueous phase to the organic phase was highly efficient,with a transfer ratio of 100%for Au(Ⅲ)and 98%for Pd(Ⅱ).Furthermore,the extraction equilibrium time for Au(Ⅲ)was just 5 min.Job's method data demonstrated that TCAET formed complexes with Au(Ⅲ)and Pd(Ⅱ)in a ratio of 2:3 and 1:1,respectively,during the extraction process.TCAET showed high selectivity toward Pd(Ⅱ)and Au(Ⅲ)over other competing metal ions.Moreover,both Au(Ⅲ)and Pd(Ⅱ)could be successfully stripped from the loaded organic phases with a 1.0 mol·L^(-1)thiourea in 0.5 mol·L^(-1)HCl and 0.5 mol·L^(-1)thiourea in 0.5 mol·L^(-1)HCl,respectively.Results obtained from five consecutive extraction-stripping cycles showed good reusability of TCAET toward Au(Ⅲ)and Pd(Ⅱ)recovery.The conclusion can provide a certain reference for thiacalixarene in the recovery of precious metal species.

Investigation of factors on a fungal biofilter to treat waste gas with ethyl mercaptan

The biofilter is cost-effective for the waste gases treatment. The bacterial is the main microorganism in the conventional biofilters. However, it faces some problems on the elimination of hydrophobic compounds. In order to overcome these problems, the biofilters with fungi were developed. The objective of this study is to investigate the factors affecting ethyl mercaptan(EM)-degradation using a fungal biofilter. A laboratory experiment was set up. The effects of loading rate, empty bed residence times(EBRT) and pH on EM degradation were investigated. Over 95% removals of EM could be achieved, under the condition of the influent loadings below 50 g/(m·h). Removal efficiencies improved to 98% with EM loading decreased to 45 g/(m·h). For long EBRT of 58 s corresponding to a flow rate of 0.3 m3/h, the EM removal efficiencies of over 98% were observed. However, when EBRT was decreased to 14 s, the removal efficiencies fell under 80%. The pH range of 3—5 was feasible to fungi.

Tailoring the mercaptan ligands for high performance inverted perovskite solar cells with efficiency exceeding 21%

Interface passivation engineering has been recognized as an effective way to simultaneously contribute to the optoelectronic characteristic and stability of perovskite solar cells(PSCs). Herein, a p-conjugated dual-ligand 1,4-phenylmercaptan(PHMT) is explored to rationally tailor the surface of perovskite film.The experimental and theoretical results show that the PHMT presents planar structure and obvious electron delocalization characteristics, which allow it to anchor on the surface of perovskite with a certain orientation, thereby promoting the transport of interface charge. Moreover, the two sulfhydryl groups in PHMT reduce the trap density of the perovskite film by passivating under-coordinated lead ions.Consequently, the PHMT-modified inverted device based on MAPbI_(3)(MA: methylammonium) achieves enhanced efficiency from 18.11%(control) to 21.11%, along with the ambient stability up to 3500 h.After being placed at 85 °C for 500 h or illuminated for 600 h, the modified device remains over 89%or 86% of initial efficiency. This discovery opens a new window for the choice of passivators to improve the performance of PSCs.

Synthesis and Adsorption Studies on Magnetic Microbeads of Polythioether-arylamine Resins

By the suspended condensation reaction of poly(choloromethylthiirane)with o-tolidine and o- dianisidine respectively, two newmicrobeads chelating resins were synthesized by usingγ-Fe_2O_3 asmagnetic core. Their adsorption properties for Hg(Ⅱ), Cu(Ⅱ), Zn(Ⅱ), Pb(Ⅱ), Au(Ⅲ), Pd(Ⅱ), Pt (Ⅳ)and Ag(Ⅰ)were investigated. Themicrobeads posses excellent adsorbability for Hg(Ⅱ) and noble metalions, and predominantly adsorbed Pd(Ⅱ)or Hg(Ⅱ)in the coexistence ofCu(Ⅱ), Zn(Ⅱ)and Mg(Ⅱ).

Green Synthesis of Aryl Thioethers through Cu-catalysed C-S Coupling of Thiols and Aryl Boronic Acids in Water

An efficient, practical, highly selective and environmentally benign method is reported for the synthesis of aryl thioethers via the coupling of thiols with aryl boronic acids in the presence of NaOH and a catalytic amount of CuSO4 at 130 ℃ using water as a green solvent. The products were obtained in moderate to excellent yields;more importantly, the use of toxic ligands and solvents was avoided. A broad range of aryl boronic acids and scalable processes make this methodology valuable and versatile for the synthesis of a broad range of aryl sulfides.

Activated Carbons Containing Dispersed Metal Oxide Particles for Removal of Methyl Mercaptan in Air

Activated carbons containing dispersed metal oxide particles were prepared by carbonization of phenol resin containing metal compounds followed by steam activation. Acetylacetonates of Fe, Mn and V, and Cu nitrate were used as the sources of metals. The removal of a small amount of methyl mercaptan (CH3SH) in air with these activated carbons was tested in a flow system. Compared with activated carbons without metal oxides, the carbons exhibited high activity for the removal of CH3SH in air. In particular, activated carbon obtained from Novolac containing 5 wt% Cu showed excellent behavior over a long time.

A thioether-functionalized pyrene-based covalent organic framework anchoring ultrafine Au nanoparticles for efficient photocatalytic hydrogen generation

Covalent organic frameworks(COFs)have lately emerged as a blooming class of potential materials for photocatalytic water splitting because of their high crystallinity,huge surface areas,and structural versatility.However,the photocatalytic performance for most pure COFs face some limitations factors,such as the significant recombination of photogenerated carriers and slow charge transfer.Herein,a novel thioether-functionalized pyrene-based COF(S_(4)-COF)was effectively produced and chosen as a support for the immobilization of ultrafine gold nanoparticles(Au NPs).S_(4)-COF photocatalyst with Au as cocatalyst demonstrates remarkable photocatalytic activity with a H_(2) generation rate of 1377μmol g^(−1) h^(−1) under visible light(>420 nm),which is ca.4.5-fold increase comparing to that of pure S_(4)-COF(302μmol g^(−1) h^(−1)).Au NPs anchored on S_(4)-COF possess an ultrafine size distribution ranging from 1.75 to 6.25 nm with an average size centered at 3.8 nm,which benefits from the coordination interaction between thioether groups and Au.Meanwhile,the produced Au@S_(4)-COF can generate a stable photocatalytic H_(2) generation during the four recycles and preserve its crystallinity structure after the stability testing.The Au NPs anchored on the S_(4)-COF photocatalyst can greatly accelerate the separation of photogenerated carriers and increase charge transfer because of the combined function of Au NPs and thioether groups.Such a method can not only prevent the aggregation of Au NPs onto thioether-containing COFs to achieve long-term photostability but also allow uniform dispersion for an ordered structure of photocatalysts.This work provides a rational strategy for designing and preparing COF-based photocatalysts for solar-driven H_(2) production.

Oxidation of Mercaptans from Light Oil Sweetening by Fe_2O_3/MgO/Al_2O_3 Supported CoPcS Catalyst

MgO/Al2O3 and Fe2O3/MgO/Al2O3 solid bases were prepared through mixing method. After sulfonated cobalt phthalocyanine （CoPcS） being supported on these solid bases, the catalytic performance of these catalysts was evaluated by means of mercaptan oxidation reaction. The samples were characterized by X-ray diffraction （XRD）, CO2 temperature-programmed desorption （CO2-TPD）, FTIR spectroscopy, and X-ray photoelectron spectroscopy （XPS）. Investigation was focused on the effect of Fe2O3 on activity, crystal structure, basicity, and stability of the catalyst and also on the role of Fe2O3 in the mercaptan oxidation processes. Test results have shown that the Fe2O3/MgO/Al2O3- CoPcS catalyst has a higher initial activity and a much longer service life than the MgO/Al2O3-CoPcS catalyst. The increased types of basic sites coupled with an enhanced oxidation ability resulted from the addition of Fe2O3 have contributed to the improvement of the catalytic activity of the MgO/Al2O3-CoPcS catalyst.

Synthesis of core-shell structured polymers with inserted thioether from a multi-functional scaffold

The synthesis of a thioether inserted, core-shell structured polymer from the scaffold of hyperbranched polyglycerol (PG) was described. PG was first allyl functionalized, and in the presence of AlBN, the allyl groups further underwent radical addition to thiol compounds, thus thiol functional polyethylene oxide monomether (MPEO) were grafted onto PG. Similarly, 2-mercaptoethylammonium chloride was introduced onto PG via thiol addition, and the residual amino groups were further quaternized with decyl bromide, leading to an amphiphilic core-shell structure polymer. (c) 2007 De Cheng Wan. Published by Elsevier B.V. on behalf of Chinese Chemical Society. All rights reserved.

A Novel Method of Preparing Unsymmetrical Thioether from Disulfides

The disulfides reacted with zinc in DMF, followed by alkyl halides, giving unsymmetrical thioether in excellent yields. This reaction takes place under mild and neutral conditions.

Indium-mediated Facile Synthesis of (6-Chloropyridine-3-yl) methyl Heterocyclic Thioether Derivatives in Aqueous Media

A series of substituted (6-chloropyridine-3-yl)methyl heterocyclic thioether derivatives were prepared by indium mediating in water. The preliminary biological tests showed that compound 3d exhibited good antiviral activity.

MODIFICATION OF PALLADIUM METALLIC CATALYST WITH POLYMER-ANCHORED THIOETHER LIGANDS

A well-dispersed metallic palladium catalyst modified by polymer-anchored thioether ligands was used for the hydrogenation of cyclopentadiene to cyclopentene with high activity and selectivity in ambient condition. The evidences to show the modification of catalytic properties by polymer anchored ligands were given.

CROSS-LINKING OF AROMATIC POLY(THIOETHER)S

A novel cross-linking process using two high molecular weight aromatic poly（thioether）s, which were synthesized by the reactions of 4,4＇-thiobisbenzenethiol with 4,4＇-difluorobenzophenone and 4,4＇-difluorodiphenylsulfone, respectively, and commercially available lower molecular weight poly（p-phenylene sulfide） was investigated. These reactions were carried out in bulk by the addition of silver tetrafluroborate and α,α＇-dibromo-p-xylene at 190℃ over a period of 45 min. Furthermore, the same procedure could be modified to cross-link compression-molded films of these three polymers. The thermal and solubility behaviors of these polymers before and after cross-linking reactions, are presented.

Synthesis of Some New Thioethers and 4-Thiazolidinones Bearing 3-(Pyridine-4'-yl)-1,2,4-Triazino[5,6-<i>b</i>]Indole Moiety as Antifungal Agents

Some new asymmetric thioethers 5 and 4-thiazolidinones 6 have been obtained from condensation of 5-formyl-3-(pyridin-4'-yl)-1,2,4-triazino[5,6-b] indole (3) with halogenated aromatic amines followed by addition of thiophenol and/or cycloaddition with thiolactic acids in nonpolar solvents. Structures of the products confirmed by elemental analysis and spectral measurements. The new systems obtained were evaluated as antifungal agents.

Preparation and Properties of Vegetable-Oil-Based Thioether Polyol and Ethyl Cellulose Supramolecular Composite Films

Ethyl cellulose(EC),an important biomass-based material,has excellent film-forming properties.Nevertheless,the high interchain hydrogen bond interaction leads to a high glass transition temperature of EC,which makes it too brittle to be used widely.The hydroxyl group on EC can form a supramolecular system in the form of a non-covalent bond with an effective plasticizer.In this study,an important vegetable-oil-based derivative named dimer fatty acid was used to prepare a novel special plasticizer for EC.Dimer-fatty-acid-based thioether polyol(DATP)was synthesized and used to modify ethyl cellulose films.The supramolecular composite films of DATP and ethyl cellulose were designed using the newly-formed van der Waals force.The thermal stability,morphology,hydrophilicity,and mechanical properties of the composite films were all tested.Pure EC is fragile,and the addition of DATP makes the ethyl cellulose films more flexible.The elongation at the break of EC supramolecular films increased and the tensile strength decreased with the increasing DATP content.The elongation at the break of EC/DATP(60/40)and EC/DATP(50/50)was up to 40.3%and 43.4%,respectively.Noticeably,the thermal initial degradation temperature of the film with 10%DATP is higher than that of pure EC,which may be attributed to the formation of a better supramolecular system in this composite film.The application of bio-based material(EC)is environmentally friendly,and the novel DATP can be used as a special and effective plasticizer to prepare flexible EC films,making it more widely used in energy,chemical industry,materials,agriculture,medicine,and other fields.

Effect of Different Loadings on the Performance of Ni2P/Al2O3 Catalysts for Low-Temperature Thioethering and Selective Hydrogenation of Diolefins in Liquefied Petroleum Gas

In this study,different loadings of x%Ni_(2)P/γ-Al_(2)O_(3)(x=6%,9%,12%,15%,18%)catalysts with aluminum oxide(Al_(2)O_(3))as the carrier,nickel chloride(NiCl2)as the nickel(Ni)source,and ammonium hypophosphite(NH_(4)H_(2)PO_(2))as the phosphorus(P)source were prepared by the equal volume impregnation method to investigate the effects of different loadings on the performance of the selective hydrogenation of diolefins and thiol etherification in LPG.The physicochemical properties of the catalysts were characterized by XRD,BET,SEM,TEM,H_(2)-TPR,and XPS,and the catalytic activity of the catalysts was evaluated in a fixed-bed microreactor.The results showed that a change in the loading affected the catalyst crystalline phase structure and size,specific surface area,P coverage,active phase dispersion,and catalytic activity.At 6%,9%,and 12%loadings the catalysts had an Ni phase but there was no obvious Ni_(2)P phase in the nickel phosphide;at 15%loading a single Ni_(2)P phase was obtained,and at 18%loading both Ni_(2)P and Ni1_(2)P_(5) phases appeared.There was a P enrichment on the catalyst surface,and the higher the loading the more P species were enriched on the surface,but some of the P was lost during the catalyst reduction process due to the production of phosphine(PH3)gas.The 15%Ni_(2)P/γ-Al_(2)O_(3) catalyst had the largest Ni/Al ratio and the best dispersion.The Ni_(2)P active phase size was small at about 4.25 nm and Ni_(2)P was uniformly dispersed on the catalyst surface without agglomeration.The 15%Ni_(2)P/γ-Al_(2)O_(3) catalyst had the best catalytic activity at a pressure of 2.0 MPa,a liquid hourly space velocity(LHSV)of 3.0 h-1,and a hydrogen to hydrocarbon ratio of 12.The 1,3-butadiene conversion was 97.45%and the methanethiol removal was 100%at a temperature of 140℃.

INTERACTION OF PLASMA—LIQUID IN AN OXYGEN GLOW DISCHARGE Ⅲ.OXIDATION DESULFURIZATION OF ETHYL—THIOETHER

A few factors affecting plasma oxidation desulfurization of ethyl- thioether were investigated.Under the typical conditions,the conversion and degree of desulfurization of ethyl-thioether can be achieved up to 88% and 79% respectively.

Biobased Aromatic-Aliphatic Polyols by Thiol-Ene Reactions of Propoxylated Mercaptanized Cardanol

Aromatic-aliphatic polyols were obtained previously from the thiol-ene reactions of propoxylated cardanol with hydroxyalkyl mercaptans;these aromatic-aliphatic polyols were then utilized in the preparation of rigid polyurethane foams with excellent properties.The current work describes a variant of cardanol polyol synthesis by thiol-ene reactions in three steps.The first step is propoxylation of cardanol by reacting cardanol with propylene oxide;the second step is mercaptanization of propoxylated cardanol by reacting double bonds with hydrogen sulfide;and the third step involves the addition of the thiol groups of mercaptanized propoxylated cardanol to the double bonds of allyl alcohol,glycerol-1-allyl ether,and trimethylolpropane allyl ether.Thus,obtained polyols were characterized by standard analytical methods.Rigid polyurethane foams prepared from these polyols show promising physical-mechanical properties.The rigid polyurethane foams can be used for various applications such as thermo-insulation of freezers,storage tanks and pipes for food and chemical industries,wood substitutes and flotation materials.

INTERACTION OF PLASMA-LIQUID IN AN OXYGEN GLOW DISCHARGE Ⅱ. OXIDATION DESULFURIZATION OF ISOBUTYL MERCAPTAN

A few factors affecting plasma oxidation desulfurization of isobutyl mercaptan were investigated. Under the reasonable condition, the conversion and degree of desulfurization of isobutyl mercaptan can be achieved up to over 95% and 94％ respectively.

Effect and Influence of Aryl Mercaptanes with Various Chain Lengths on DNA/RNA and Cadmium Oxide (CdO) Nanoparticles Sandwiched Complex

CdO(cadmium oxide)nanoparticles show a strong peak of Plasmon absorption in ultraviolet-visible zone.A strong interaction exists between the surface of CdO nanoparticles and aryl mercaptan compounds.Aryl mercaptan compounds cause aggregation of CdO nanoparticles linked to DNA/RNA(eoxyribonucleic acid/ribonucleic acid)and hence,lead to widening of peak Plasmon of CdO nanoparticles surface at 550 nm and emerge a new peak at higher wavelength.In the current project,this optical characteristic of CdO nanoparticles is used to investigate interaction time between different aryl mercaptanes and CdO nanoparticles.The results showed that aryl mercaptan compounds with shorter chain length interact faster with CdO nanoparticles.Therefore,a simple and fast method for identification of aryl mercaptanes with various chain lengths using red shift in surficial Plasmon absorption is presented.