Sulfinyl-Mediated Stereoselective Functionalization of Acyclic Conjugated Dienes

The chemo- and stereocontrolled functionalization of conjugated sulfinyl dienes in a cascade process that involves a conjugate addition, diastereoselective protonation and a [2,3]-sigmatropic rearrangement is reported. Enantioenriched 1,4-diol and 1,4-aminoalcohol derivatives are obtained in a very straightforward manner. Further functionalization of these structures, including highly stereoselective epoxidation, dihydroxylation and the stereodivergent synthesis of several polyols in a controlled fashion is described.     

Synthesis,Structure, Reactivity and Catalytic Implications of a Cationic,Acetylide-Bridged Trigold–JohnPhos Species

The cationic complex [(JohnPhos–Au)₃(acetylide)][SbF₆] (JohnPhos=(2-biphenyl)di-tert-butylphosphine, L1) has been characterised structurally and features an acetylide–trigold(I)–JohnPhos system; the trinuclear–acetylide unit, coordinated to the monodentate bulk phosphines, adopts an unprecedented μ,η¹,η²,η¹ coordination mode with an additional interaction between distal phenyl rings and gold centres. Other cationic σ,π-[(gold(I)L1)₂] complexes have also been isolated. The reaction of trimethylsilylacetylene with various alcohols (iPrOH, nBuOH, n-HexOH) catalysed by cationic [Au^IL1][SbF₆] complexes in CH₂Cl₂ at 50 °C led to the formation of acetaldehyde acetals with a high degree of chemo- and regioselectivity. The reaction mechanism was studied, and several organic and inorganic intermediates have been characterised. A comparative study with the analogous cationic [Cu^IL1][PF₆] complex revealed different behaviour; the copper metal is lost from the coordination sphere leading to the formation of cationic vinylphosphonium and copper nanoparticles. Additionally, a new catalytic approach for the formation of this high-value cationic vinylphosphonium has been established.     

Ion-Functionalized Silver(I) Carboxylates: Synthesis and Application in Ru-Catalyzed Olefin Metathesis Reaction

Russian Journal of General Chemistry - The Grubbs–Hoveyda catalysts have a wide range of applications in catalyzed formation of the carbon-carbon double bonds. In this study, several...     

Review on synthesis methods to obtain LiMn2O4-based cathode materials for Li-ion batteries

Journal of Solid State Electrochemistry - Lithium manganese spinel (LiMn2O4) is considered a promising cathode material for lithium-ion batteries (LIBs). Its structure, morphology, and...     

Polypyrrole modified hierarchical porous CoS2@RGO aerogel electrode for ultrafast sodium storage

Journal of Solid State Electrochemistry - CoS2 nanooctahedrons homogeneously encapsulated by hierarchical porous-reduced graphene oxide and polypyrrole thin film are constructed via a simple...     

Combined Spectroscopic and TD-DFT Analysis to Elucidate Substituent and Acidochromic Effects in Organic Dyes: A Case Study on Amino- versus Nitro-Substituted 2,4-Diphenylquinolines

A combined spectroscopic and TD-DFT case study was performed, to identify a robust method to calculate the complex near UV/Vis absorption spectra of various amino- vs. nitro-substituted 2,4-diphenylquinolines, which vary strongly under neutral and successively acidic conditions. For this, different DFT functionals were tested for geometry optimization and the TD part to calculate the neutral and different protonated species in a fast screening approach, i. e. using single point calculations in an implicit solvent. Offset-corrected M06HF, hitherto only applied to polymers, was identified as a suitable method to reproduce the absorption spectra in a reasonable fashion for all different substitution pattern and all different protonated species at different pH values; moreover, the method properly predicts the energetic ordering of low-lying n-π* and ππ* transitions, which is decisive for the non-/emissive nature of the different compounds. In all, this might provide a valuable tool for computer-aided design of related classes of compounds.     

A semi-automatic method for measuring interferometry fringes: prototype design and first results

A device for automatically obtaining the information contained in holographic interferometry fringes is proposed. The method may be applied to any kind of interferometric fringes. Accuracy has been demonstrated by contrasting the results obtained with our prototype system and those with the single-beam speckle interferometry technique for the measurement of displacements in a plane. The results show good correlation between the two series of measurements.     

XeCl准分子激光能量提取研究

在高功率准分子激光系统建设中,希望能获得较短的脉冲宽度和尽量多的激光能量。实验研究了不同注入水平下,脉冲时间间隔对脉冲链放大波形和放大器提取效率的影响;基于四能级速率方程和准分子反应动力学建立了准分子激光放大模型,计算了多种注入方式下种子光的放大过程,对关键参数给出了量化描述,得到与实验相符的计算结果。研究结果显示:脉冲序列间隔为9.3 ns时,可获得约95%的连续注入情形下放大能量;对该准分子激光系统来讲,9.3 ns是比较合适的脉冲间隔。