Iodinated Biaryls Synthesized by the Direct Dehydrodimerization of Iodoarenes Using Phenyliodine(III) Bis(trifluoroacetate) (PIFA)

Multiply iodinated biaryls can be prepared in yields up to 75% by direct oxidative coupling reaction of the iodinated arenes. The PIFA‐mediated dehydrodimerization is superior to all other known methods. The developed protocol is reliable and easy to perform.     

Anodic oxidation of bis(organylchalcogeno)acetylenes

The electrochemical oxidation of bis(organylchalcogeno)acetylenes has been examined in organic solvents. With symmetrical ones, R---Z---CC---Z---R (1) (Z=S, Se), and with unsymmetrical ones, R¹---S---CC---Z---R² (2) (Z=Se), in macroscale electrolyses the α-diesters R¹---Z(S)---CO---CO---Z---R² were obtained as the main products. If Z=Te, from 1 and 2, reactions were more complex and the cleavage of the C---Te bond was always observed.     

Electrochemical behavior of europium (III) in N-butyl-N-methylpyrrolidinium bis(trifluoromethylsulfonyl)imide

N-butyl-N-methylpyrrolidinium bis(trifluoromethylsulfonyl)imide (BMPyNTf₂) was synthesized and characterized by CHNS elemental analysis, ¹H and ¹³C NMR and IR spectroscopy. Europium tris[bis(trifluoromethylsulfonyl)imide] (Eu(NTf₂)₃) was prepared and studied for the electrochemical behavior of Eu(III) in BMPyNTf₂ at glassy carbon and stainless steel working electrodes at 298-373 K by cyclic voltammetry, chronopotentiometry and chronoamperometry. Cyclic voltammogram of Eu(III) in BMPyNTf₂ consisted of a quasi-reversible cathodic wave at −0.45 V (vs. Fc/Fc⁺, 373 K), which could be attributed to the reduction of Eu(III) to Eu(II) and an irreversible wave at −2.79 V (vs. Fc/Fc⁺) due to reduction of Eu(II) to Eu(0). The diffusion coefficient of Eu(III) in BMPyNTf₂ was determined to be in the range of ∼10⁻⁷ cm² s⁻¹ by various electrochemical methods and the charge transfer rate constant was determined to be ∼10⁻⁵ cm s⁻¹ by cyclic voltammetry.     

非均相Mn(Ⅲ)-甲苯氧化反应的动力学

研究了非均相Mn(Ⅲ）－甲苯氧化反应的动力学.了Mn(Ⅲ）（指MnSO4^ )的歧化反应的因素并结合平行反应的原理，建立了反应动力学方程模型。通过测定不同温度，酸度下，歧化反应中[MnSO4^ ]的浓度变化和[PhCH3]在Mn(Ⅲ）－甲苯氧化反应中的浓度变化，发现Mn(Ⅲ）的歧化反应在此条件下为零级反应，数据经数学处理后，求得氧化反应的速率常数，反应级数，反应活化能以及动力学微分方,同时对该反应的机理作了相应的推导。结果显示，由平行反应模型所得的动力学数据与Arrhenius's定理完全一致。     

Electrochemical reduction of Gd(III) and Nd(III) on reactive cathode material in molten fluoride media

The electrochemical reduction of two lanthanides (neodymium Nd and gadolinium Gd) was investigated in the 800–950 °C temperature range on nickel and copper electrodes. These materials react with lanthanides (Ln) to form intermetallic compounds. The formation mechanism of the alloys was determined by coupling electrochemical techniques and Scanning Electron Microscopy (SEM) after electrolyses runs; this also allowed the identification of the binary compounds formed. In addition, from the electrochemical results, we calculated the Gibbs energies of Nd/Ni, Gd/Ni, Gd/Cu and Nd/Cu.     

邻(对)羟基苯乙烯酮的合成

介绍了邻（对）羟基苯乙烯酮的制备方法。该法采用丙酮和邻（对）羟基苯甲醛在稀碱存在下，于20℃-25℃进行醛酮缩合反应，合成工艺简单，收率高。用^1HNMR,^13CNMR分析，产品纯度高。     

固载手性双(口恶)唑啉的合成及其在不对称合成中的应用

本文综述了近年来固载手性双噁唑啉的合成及其金属配合物作为手性催化剂在催化不对称反应中的研究进展。     

脂肪二酸类手性双(口恶)唑啉配体的合成进展

总结了近年来用于不对称催化的脂肪二酸类手性双噁唑啉配体的合成方法,该类配体可由丙二酸、乙二酸与丁二酸的酰氯和二酯或二元腈与相应的氨基醇反应得到。     

哌啶类双氨基雄甾烷类化合物的合成及其活性研究

在对双氨基雄甾烷类化合物构效关系研究的基础上,合成了2个哌啶类双氨基雄甾烷类化合物,并对合成的过程和活性测定的结果进行了分析,以期发现更加有效或毒副作用更小的肌松药。化合物的结构均经1H NMR和13C NMR确证。     

Synthesis and characterization of the bis(trithioperoxybenzoate)(dithiobenzoate)rhenium(III) hetero complex

Reduction-substitution reactions between high valent [ReOCl₄][NBu₄] or [ReNCl₄][NBu₄] complexes and the phenyldithiocarboxylate piperidinium salt lead to a novel rhenium(III) complex with mixed coordination sphere. The structure of this compound [Re(S₃CPh)₂(S₂CPh)], containing two trithioperoxybenzoate and one dithiobenzoate ligands, has been elucidated by NMR, mass spectrometry and X-ray diffraction analysis.     

A dinuclear copper(II) compound of a bis(imidazole)-containing tripodal ligand: Crystal structure and EPR spectroscopic studies

The dinuclear compound, 1, with the molecular formula of [Cu₂(H₃L)₂(ClO₄)₂][Cu₂(H₃L)₂(MeCN)₂](ClO₄)₆ was prepared by the reaction of [bis-(1H-imidazol-2-yl)-methyl]-pyridin-2-yl-methylamine (H₃L) with copper(II) perchlorate. The asymmetric unit of the crystal structure of 1 contains two dinuclear units, [Cu₂(H₃L)₂(ClO₄)₂]²⁺ and [Cu₂(H₃L)₂(MeCN)₂]⁴⁺ (abbreviated as 1^ClO4 and 1^MeCN), respectively, and they are linked through hydrogen bonding between the oxygen atom from the axial coordinated perchlorate anions and one of the neighboring imidazole rings from 1^MeCN. EPR spectroscopic studies of 1 in MeOH by addition of bridging ligands including NaN₃ and NaOH were carried out and the reaction process was discussed.     

Thioetherglycidyl resins. III. Products of condensation of bis(4-mercaptophenyl)ether and bis(4-mercaptophenyl)methane with epichlorohydrin

Thioetherglycidyl resins produced by condensation of bis(4-mercaptophenyl)ether and bis(4-mercaptophenyl) methane with epichlorohydrin were obtained by heterophase alkaline condensation. To define the optimal conditions of condensation, the following factors that influence the process were studied: the kind of organic phase and the mole ratios of epichlorohydrin:mercaptan, alcohol:mercaptan, and alkaline hydroxide:mercaptan. For all syntheses yield and the epoxide content were found. The structure of thioetherglycidyl resins with the highest epoxide content was determined by elementary analysis, infrared IR, and NMR spectra. The physical and chemical properties were also defined. The investigations covered the determination of some properties of resins, cured chemically or thermally with different curatives and thermal and mechanical properties of the cured compounds.     

常压高效合成双(烷基聚氧乙烯基)仲胺

针对仲胺基聚醚合成存在产率低、反应条件苛刻等问题,以端伯胺基C12～14烷基聚乙二醇醚(A/C12～14E5)为原料,通过伯胺在常压条件的分子间脱氨耦合,高效地合成了双(C12～14烷基聚氧乙烯基)仲胺(S/C12～14E5).探究了耦合温度、催化剂用量、氢气流量及反应时间对S/C12～14E5选择性的影响.结果表明,...     

Spectroscopic Study of Neodymium(III) in Sodium Tellurite Glass

The local environment of Nd-O in a sodium tellurite glass was elucidated as a function of Nd₂O₃ concentration, from 0.1 to 2.5 mol%, using optical spectroscopy. The Judd-Ofelt (J-O) theory was used to determine the oscillator strength parameters (J-O parameters) of the glasses. According to the J-O parameters, a significant change in the local environment of Nd-O was suggested for the glass containing 1 mol% Nd₂O₃; the asymmetry of the Nd-O crystal field was shown to be at a maximum and the bond covalency at a minimum. The results were further supported by a significant shift of the structural hypersensitive band of the glass with 1 mol% Nd₂O₃, as compared with those of the other glasses.     

Role of Structural Fe(III) and Iron Oxide Nanophases in Mullite Coloration

Six mullite samples, derived from heat-treated natural kaolinites with various iron content, were investigated and compared to synthetic monophasic mullite. They were analyzed by X-ray diffraction, diffuse reflectance spectroscopy, and electron paramagnetic resonance. To quantify mullite coloration, the CIE colorimetric system was used. In contrast to synthetic mullite, samples showed charge transfer bands involving O²⁻ and Fe³⁺ ions as well as ferric crystal-field transitions due to Fe³⁺ ions in iron oxide nanoparticles. Absorption edges showed red shifts. The resulting yellowness, saturation of which increased with the content of iron oxide nanoparticles, is direct evidence for the coloring effect of Fe³⁺ ions.     

Novel luminescent europium(III) complexes covalently bonded to bis(phosphino)amine oxide functionalized MCM-41

A novel organo-functionalized mesoporous MCM-41 type of hybrid materials MCM–Si–DPBB was synthesized by co-condensation of bidentate Si(OR)₃ substituted N,N-2-diphenyloxyphosphine-4-bromomethyl-benzenamine (Si–DPBB) and tetraethoxysilane (TEOS) in the presence of the cetyltrimethylammonium bromide (CTAB) surfactant as template. Its ternary europium complex covalently bonded to the silica-based network MCM–Si–DPBB–Eu was also prepared by introduction the Eu(DBM)₃(H₂O)₂ into the hybrid materials. The hybrid material MCM–Si–DPBB–Eu has strong luminescence, and when excited by the ligands absorption wavelength (386 nm), it displays the emission of the Eu^{3+ 5}D₀-⁷F_J (J = 0, 1, 2, 3 and 4) transition lines due to the efficient energy transfer from the ligands to Eu³⁺.     

Computer-Aided (In Silico) Modeling of Cytochrome P450-Mediated Food–Drug Interactions (FDI)

Modifications of the activity of Cytochrome 450 (CYP) enzymes by compounds in food might impair medical treatments. These CYP-mediated food–drug interactions (FDI) play a major role in drug clearance in the intestine and liver. Inter-individual variation in both CYP expression and structure is an important determinant of FDI. Traditional targeted approaches have highlighted a limited number of dietary inhibitors and single-nucleotide variations (SNVs), each determining personal CYP activity and inhibition. These approaches are costly in time, money and labor. Here, we review computational tools and databases that are already available and are relevant to predicting CYP-mediated FDIs. Computer-aided approaches such as protein–ligand interaction modeling and the virtual screening of big data narrow down hundreds of thousands of items in databanks to a few putative targets, to which the research resources could be further directed. Structure-based methods are used to explore the structural nature of the interaction between compounds and CYP enzymes. However, while collections of chemical, biochemical and genetic data are available today and call for the implementation of big-data approaches, ligand-based machine-learning approaches for virtual screening are still scarcely used for FDI studies. This review of CYP-mediated FDIs promises to attract scientists and the general public.     

双(4-氟苯基)苯基氧膦磺酸钠盐的合成及表征

以双(4-氟苯基)苯基氧膦为起始原料,20%发烟硫酸为磺化试剂,分别合成了双(3-磺酸钠-4-氟苯基)-3’-磺酸钠苯基氧膦、4-氟苯基-(3’-磺酸钠-4’-氟苯基)-3″-磺酸钠苯基氧膦和双(4-氟苯基)-3’-磺酸钠苯基氧膦等3种单体,实验方法操作简便、反应后处理简单且收率较高,适用于产品的大规模制备。