Efficient synthesis of unsymmetrical diaryl thioethers via TBAF-mediated denitrative substitution of nitroarenes with PhSTMS under mild and neutral conditions

Tetrabutylammonium fluoride(TBAF) effectively facilitated a denitrative substitution reaction of electron-deficient nitroarenes with phenylthiotrimethylsilane(PhSTMS) under mild and base-free neutral conditions at room temperature,providing a practical and efficient synthesis of useful unsymmetrical diaryl thioethers.Nitroarenes bearing ortho-and para-positioned electron-withdrawing groups are the most reactive substrates,indicating that this reaction most possibly proceeded via the nucleophilic aromatic substitution(S_NAr) mechanism.     

Design, synthesis and insecticidal activity of novel anthranilic diamides with benzyl sulfide scaffold

A series of novel anthranilic diamides with benzyl sulfide scaffold were synthesized,in which N-pyridylpyrazole moiety generally regarded as key pharmacophore was abandoned.The target compounds were characterized by ¹H NMR,¹³C NMR,¹⁹F NMR and HRMS.The preliminary bioassays indicated that half of the title compounds were endowed with good insecticidal activities against armyworm（Mythimna sepatara） at the concentration of 500 mg/L,Exhilaratingly,the synthesized compound 3a was also active against Tetranychus cinnabarinus at 100 mg/L.The difference in activities between the target compounds was influenced by the substituents,which provided some hints for further investigation on structure modifications.     

Synthesis of symmetrical 1, 3-diynes via tandem reaction of (Z)-arylvinyl bromides in the presence of DBU and CuI

Microwave-assisted tandem reaction of(Z)-arylvinyl bromides involving an elimination and homocoupling in the presence of DBU and Cul in DMF affords a variety of symmetrical 1,3-diynes in good to excellent yields.This tandem process,eliminating the need of volatile and savory terminal alkynes,provides an alternative to the conventional homocoupling methods for the synthesis of symmetrical 1,3-diynes.     

Chiral Sulfinamide-Olefin Ligands: Switchable Selectivity in Rhodium-Catalyzed Asymmetric 1,2-Addition of Arylboronic Acids to Aliphatic α-Ketoesters

Simple and readily available chiral N‐(sulfinyl)allylamines have been developed as efficient novel ligands for the rhodium‐catalyzed enantioselective 1,2‐addition of arylboronic acids to challenging aliphatic α‐ketoesters. By employing the linear or branched sulfinamide‐olefin ligands, interesting enantioselectivity as well as regioselectivity reversal in the related asymmetric additions were observed.     

Preparation of Polymer-Functionalized Iron Oxide Nanoparticles and Their Biomedical Properties

Superparamagnetic iron oxide nanoparticles with narrow size distributions were successfully prepared in large scale by a facile one‐pot synthetic method in the presence of hydrophilic polymers, such as polyethylene glycol diacid (HOOC‐PEG‐COOH) and poly(acrylic acid) (PAA). The as‐prepared products were investigated in detail by powder X‐ray diffraction (XRD), thermogravimetric analyses (TGA), transmission electron microscopy (TEM), high‐resolution transmission electron microscopy (HRTEM), dynamic light scattering (DLS), and vibrating sample magnetometer (VSM). The interaction between polymers and iron oxide nanoparticles was investigated using Fourier transform infrared spectrometry (FT‐IR). The results show that polymers can be attached onto the surface of iron oxide nanoparticle by bridging coordination and monodentate fashion, respectively. The interaction affects iron oxide nanoparticle properties significantly, such as XRD diffraction intensity, hydrodynamic diameter, isoelectric point, and saturation magnetization. Furthermore, the results of in vitro experiments indicated that iron oxide‐PEG‐COOH nanoparticle is more cytotoxic than iron oxide‐PAA nanoparticle due to different coordinating modes.     

A new family of supramolecular multiferrocenyl rhomboids:Synthesis,characterization,and their electrochemical behavior

Two novel,supramolecular,multiferrocenyl rhomboids 5 and 6 have been successfully constructed from newly designed 60 ferrocenyl donor precursor 1 via coordination-driven self-assembly.The structures of all multiferrocenyl rhomboids were characterized by multinuclear NMR(¹H and ³¹P),CSI-TOF-MS, and PM6 semi-empirical molecular simulation,and their electrochemical behaviors have been investigated.     

膦配体取代的乙基乙撑双铁配合物的合成、晶体结构及电化学催化性能

以母体配合物[Fe₂(CO)₆(μ-SCH₂CH(CH₂CH₃)S)](1)分别与三(2-呋喃基)膦、二苯基丙基膦、双(二苯基膦)乙炔、1,2-双(二苯基膦基)苯和脱羰试剂Me₃NO·2H₂O反应,制备了单取代配合物[Fe₂(CO)₅(L)(μ-SCH₂CH(CH₂CH₃)S)](L=P(2-C₄H₃O)₃,2;Ph₂PCH₂CH₂CH₃,3)、桥联配合物{[Fe₂(CO)₅(μ-SCH₂CH(CH₂CH₃)S)]2(Ph₂PC≡CPPh₂)}(4)和螯合配合物[Fe₂(CO)₄(κ²-(Ph₂P)₂(1,2-C₆H₄))(μ-SCH₂CH(CH₂CH₃)S)](5)。配合物2~5经元素分析、红外光谱、核磁共振氢谱和磷谱表征,并进一步得到单晶X射线衍射的确证。电化学研究表明,在弱酸HOAc作为质子源存在的情况下,这些配合物可以实现催化质子还原产生氢气的功能。     

石墨炉原子吸收法测定PU材料中的铬

采用微波消解技术进行样品前处理,建立了石墨炉原子吸收法测定PU材料中铬含量的方法。在波长429.0 nm下,利用石墨炉程序升温测定,狭缝设为0.5 nm,塞曼效应作为背景校正。标准工作曲线线性良好,相关系数r=0.9986,方法检出限为0.051μg/L,测定结果的相对标准偏差为3.78%,加标回收率为92%～120%(n=6)。该方法简便、可行,适用于PU材料中铬的测定。     

High efficiency palladium catalysts supported on multi-wall carbon nanotubes synthesized with 1,3-bis(diphenylphosphino) propane for ethanol oxidation

In this paper, a facile and effective method is introduced to prepare palladium electrocatalysts for the oxidation of ethanol in alkaline media. According to the transmission electron microscopy measurement, the as-prepared Pd nanoparticles with the average particle size of 2.5 nm are evenly deposited on the surface of the multi-wall carbon nanotubes by using 1,3-bis(diphenylphosphino) propane as a special additive. Electrochemical measurements demonstrate that the as-prepared catalyst exhibits good electrocatalytic activity and stability for the electrooxidation of ethanol.     

Modeling and Simulation of Bonding and Optical Characters of Ternary Nanocrystals

In this paper, conformations of the ternary structures ZnSe(Te), ZnS(Te), ZnS(Se), CdSe(Te), CdS(Te) and CdS(Se) were optimized, and their orbital, spectra have been investigated at the B3LYP/LANL2DZ level. First, we have found some rules which agreed with experimental results. HOMO–LUMO gaps, WBI values and the wavelengths of the absorption peaks of ternary structures changed gradually with the ratio of Te, Se and S atoms in ternary structures. Second, analysis of Raman spectra revealed that doped structures had the spectra of two relevant binary clusters. Namely, Raman spectra of ternary ZnSe(Te) clusters had the Raman peaks of ZnSe and ZnTe. In this way, with the help of the Raman spectra, the formations of the ternary structures can be determined in experiment. This was important to estimate during synthesis progress. Finally, calculated results have proved that ZnS and CdS structures had the shorter wavelengths of the absorption peaks, the higher excited energies of singlets, and good stability.