Planar Tetracoordinate Silicon in Organic Molecules As Carbenoid-Type Amphoteric Centers: A Computational Study

Designing and synthesizing a stable compound with a planar tetracoordinate silicon (ptSi) center is a challenging goal for chemists. Here, a series of potential aromatic ptSi compounds composed of four conjugated rings shared by a centrally embedded Si atom are theoretically designed and computationally verified. Both Born–Oppenheimer molecular dynamics (BOMD) simulations and potential energy surface scannings verify the high stability and likely existence of these compounds, particularly Si-16-5555 (SiN₄C₈H₈) with 16 π electrons, under standard ambient temperature and pressure. Notably, the Hückel aromaticity rule, which works well for single rings, is inconsistent with the high stability of Si-16-5555 where the 16 p electrons are spread over four five-membered rings fused together. Bonding analyses show that the strong electron donation from the peripheral 12-membered conjugated ring with 16 π electrons to the vacant central atomic orbital Si 3p_z leads to the stabilization for both the ptSi coordination and planar aromaticity. The partial occupation of Si 3p_z results in the peculiar carbenoid-type behaviors for the amphoteric center. By modulating the electron density on the ring with substituent groups, we can regulate the nucleophilic and electrophilic properties of the central Si.     

带变量核的广义高阶Marcinkiewicz积分交换子在Herz型Hardy空间的有界性

设A是R~n上的一个m阶可导函数,且D~λA∈Λ_β(0β1,|λ|=m),Ω(x,z)∈L~∞(R~n)×L~s(S~(n-1))(sn/(n-β))是零阶齐次函数且关于变量z满足消失条件.该文证明了广义高阶Marcinkiewicz积分交换子μ_Ω~A及其变形μ_Ω~A在Herz型Hardy空间的有界性.     

Application of heating microscopy to the study of thermal behaviour of ZnO–P2O5–WO3 glasses

The effect of WO₃ on thermal behaviour and thermal stability of ZnO–P₂O₅–WO₃ glasses prepared in compositional series (100 ? x)[0.5ZnO–0.5P₂O₅] ? xWO₃ (x = 0–60) was investigated by heating microscopy and the results were correlated with the results determined by conventional thermodilatometry and differential thermal analysis. Thermoanalytical studies showed that the glass transformation temperature and dilatation softening temperature increase with increasing WO₃ content while thermal expansion coefficient decreases. The highest stability towards crystallization possess glasses containing 20–30 mol% WO₃. Major compounds formed by the crystallization of the glasses were Zn(PO₃)₂, WO₃ and W₁₈P₂O₅₉. The values of sphere temperature, hemisphere temperature and flow temperature obtained using heating microscopy were strongly influenced by the degree of crystallization process at the sintering.     

Comparative pyrolysis upcycling of polystyrene waste: thermodynamics, kinetics, and product evolution profile

Pyrolysis is one important way to treat polystyrene waste and upcycle it into useful materials. A comparative pyrolysis study of virgin polystyrene (VPS) and two types of commonly used polystyrene products, expanded polystyrene (EPS) and polystyrene container (CPS) was carried out. Various values were found in the thermodynamic study and kinetic study of VPS, EPS, and CPS pyrolysis, suggesting distinct thermal degradation characteristics of these materials. The energy barrier order of the pyrolysis processes was EPS, CPS, VPS, showing activation energy of 230, 219, and 145 kJ mol^?1, respectively. The order of amount of heat absorbed was EPS, CPS, VPS, with enthalpy of 224, 213, and 139 kJ mol^?1, respectively. The reaction favorability order was EPS, CPS, and VPS with Gibbs free energy of 118, 132, and 210 kJ mol^?1, respectively. Thermogravimetric analysis indicated the use of high heating rate would increase the reaction rate and shorten the reaction time. Product evolution profiles showed that VPS and CPS pyrolysis produced mainly aromatics, while EPS pyrolysis produced aromatics at the initial phase of the reaction and aliphatic hydrocarbon at the latter phase. The diverse pyrolysis behaviors of VPS, EPS, and CPS demonstrated that an examination on different polystyrene materials was desired to optimize the pyrolysis conditions and product distribution, and thus benefit the process of valuable materials recovery.     

One-Pot Synthesis of 1-Alkynylphosphonates

1-Alkynylphosphonates 3 are prepared in a one-pot procedure from diethyl phosphorochloridates 2 and alkynyllithiums 1, which are readily generated by the reaction of 1-alkynes with n-BuLi.     

Synthesis and properties of near IR induced self-healable polyurethane/graphene nanocomposites

A series of self-healable polyurethane (SHPU)/modified graphene (MG) nanocomposites were synthesized from poly(tetramethylene glycol) (PTMG) and 4,4′-methylene diphenyl diisocyanate (MDI) with minute amounts (0–1 wt%) of MG which was chemically modified graphene oxide (GO) with phenyl isocyanate and reduced in the presence of phenylhydrazine.     

Detailed study of a two component smectic 4TPB–8OCB system with a nematic gap. Phase diagram and viscosity study

Abstract

The phase diagram of a two component system composed of two smectic compounds: 4-octyloxy-4′-cyanobiphenyl (8OCB) and 4-isothiocyanatophenyl 4-butylbenzoate (4TPB) was investigated. Three Miesowicz viscosity coefficients η₁, η₂, η₃ and the refractive indices at different temperatures as well as the enthalpies of the phase transitions were measured. It was stated, that the properties of the induced nematic phase, for example, the nematic phase existing between two smectic regions, are the same as the ones observed in the case of low viscosity nematic mesogens.     

埃罗替尼的合成

以N,N-二甲基甲酰胺和硫酸二甲酯反应生成的亚胺盐与3-乙炔基苯胺进行亲核反应及甲醇的消去,获得了制备埃罗替尼所需的重要中间体N’-(3-乙炔基苯基)-N,N-二甲基甲脒,收率为75.8%。再以此中间体与2-氨基-4,5-二(2-甲氧基乙氧基)苯甲腈通过Dimroth重排反应方便地制得了抗肿瘤药物埃罗替尼,总收率(以3-乙炔基苯胺计)为56.5%。与以往合成埃罗替尼的方法相比,该方法更经济、更绿色。     

A p‐Quinodimethane‐Bridged Porphyrin Dimer

A p‐quinodimethane (p‐QDM)‐bridged porphyrin dimer 1 has been prepared for the first time. An unexpected Michael addition reaction took place when we attempted to synthesize compound 1 by reaction of the cross‐conjugated keto‐linked porphyrin dimers 8 a and 8 b with alkynyl/aryl Grignard reagents. Alternatively, compound 1 could be successfully prepared by intramolecular Friedel–Crafts alkylation of the diol‐linked porphyrin dimer 14 with concomitant oxidation in air. Compound 1 shows intense one‐photon absorption (OPA, λ_max=955 nm, ε=45400 M ^?1 cm^?1) and a large two‐photon absorption (TPA) cross‐section (σ⁽²⁾_max=2080 GM at 1800 nm) in the near‐infrared (NIR) region due to its extended π‐conjugation and quinoidal character. It also exhibits a short singlet excited‐state lifetime of 25 ps. The cyclic voltammogram of 1 displays multiple redox waves with a small electrochemical energy gap of 0.86 eV. The ground‐state geometry, electronic structure, and optical properties of 1 have been further studied by density functional theory (DFT) calculations and compared with those of the keto‐linked dimer 8 b . This research has revealed that incorporation of a p‐QDM unit into the porphyrin framework had a significant impact on its optical and electronic properties, leading to a novel NIR OPA and TPA chromophore.     

Dynamic Electrosorption Analysis as an Effective Means to Characterise the Structure of Bulk Graphene Assemblies

Restacking of graphene sheets to a graphite‐like structure is a prevailing problem that is known to compromise the performance of individual graphene sheets in an assembled bulk form. To address this common problem efficiently and monitor the structure and quality of graphene products comprehensively, it is highly desirable to develop reliable metrology techniques for characterising graphene‐based materials on a bulk assembly level and in a quantitative manner. Here, by revisiting the physicochemical principle of electrosorption, we propose a simple electrochemical approach, namely dynamic electrosorption analysis (DEA), as an easily accessible and effective technique for evaluation of the self‐stacking behaviour of graphene. Taking multilayered chemically converted graphene films as a model, we demonstrate that the DEA technique can effectively reveal very subtle variation in accessible surface area and pore size of graphene assemblies in the liquid phase and thus can provide useful insights to the experimental design relating to restacking control. This work also reveals the huge effect some routine processing conditions, such as heat treatment and drying, can have on the structure and performance of graphene‐based bulk materials, providing useful guidance for future manufacturing of this class of materials.